Ion-molecule reactor and device for analyzing complex mixtures

Abstract

An ion-molecule reactor for generating analyte ions from an analyte, comprising: a) a reaction volume in which reagent ions can interact with the analyte to form analyte ions; b) at least one analyte inlet for introducing the analyte into the reaction volume along an inlet path, wherein preferably the inlet path extends substantially along at least a first part of a predetermined transport path in the reaction volume; c) at least one reagent ion source and / or at least one reagent ion inlet for supplying reagent ions to the reaction volume; d) optionally, at least one ion guide comprising an electrode assembly configured to generate an alternating electric field, magnetic field, and / or electromagnetic field, the electric field, magnetic field, and / or electromagnetic field allowing guiding of at least the reagent ions and / or analyte ions through the reaction volume along at least a part of the predetermined transport path, preferably along the entire transport path. A sampler is also provided, which includes one or more chambers, wherein each chamber is configured to receive respective samples and includes an inlet and an outlet such that a gaseous fluid stream can pass through each chamber.

Description

Technical Field

[0001] The present invention relates to an ion-molecule reactor for generating analyte ions from an analyte, in particular an ion-molecule reactor for use with a mass spectrometer, and a corresponding method for generating analyte ions and for analyzing a sample (in particular a cork). Other aspects of the present invention relate to a mass spectrometer, a kit including an ion-molecule reactor, an apparatus for analyzing a sample, and the use of an ion-molecule reactor in mass spectrometry for analyzing a gaseous mixture containing at least one analyte and for analyzing whether a cork is contaminated with cork taint. Background Art

[0002] Mass spectrometry is an analytical technique widely used in many different technical fields for identifying and quantifying various substances or compounds of interest (so-called analytes) in pure samples as well as complex mixtures.

[0003] Mass spectrometry generally involves correspondingly measuring the mass-to-charge ratio of ionized analytes or analyte ions. Thus, in a first step, the analyte (usually a neutral atom or molecule) needs to be ionized and transferred into a mass analyzer. Therefore, chemical ionization is particularly advantageous because the technique is selective and thus can achieve very low detection limits, resulting in minimal fragmentation as well as a high retention of molecular properties and analyte structure.

[0004] In chemical ionization, ionized analytes are generated by the collision of the analyte with reagent ions or primary ions that are usually already generated in a reagent ion source. In the reagent ion source, the reagent ions can be generated, for example, from a reagent gas (such as methane, ammonia, water, nitrogen oxides, oxygen, etc.) by electron ionization, plasma, electromagnetic radiation (such as x-rays) or radioactive radiation.

[0005] However, the efficiency of providing ionized analytes by chemical ionization essentially depends on three aspects: (1) the generation of primary ions or reactant ions; (2) the reaction of the primary ions with the analyte; and (3) the transfer of the analyte ions to the mass analyzer. In this regard, various experimental devices and instruments are known:

[0006] US 5,175,431 (Georgia Tech Research Corporations) discloses a high-pressure interface device for connecting a gas chromatograph to a mass spectrometer. In this system, in a low-temperature cleaning buffer gas or carrier gas layer flowing in a fluid tube, trace gases are ionized by radioactive radiation. As a radioactive radiation source, radioactive material can be, for example, coated on a ring inside the fluid tube or placed on an injection needle for the analyte. Thereby, the analyte is introduced axially into the fluid tube in the laminar flow region such that the analyte is ionized when interacting with the ionized trace gases and transferred to the outlet of the fluid tube.

[0007] US2014 / 0284204 A1 (Airmodus OY, University of Helsinki) describes an apparatus for ionizing molecules and clusters in a sample gas by chemical ionization before the sample gas enters an analyzer, such as a mass analyzer. Thereby, a reagent gas enters an ion molecule reactor through an inlet provided on one side of a chamber and is ionized with a single x-ray source. The sample gas is introduced into the chamber through another inlet. This inlet is oriented along the longitudinal axis of the ion molecule reactor and perpendicular to the inlet of the reagent gas. Also in this apparatus, a laminar sheath gas flow is established between the sample gas and the wall structure of the apparatus to direct the sample gas and reagent ions. The trajectory of the reagent ions can be configured to bend inward from one side of the chamber and bend towards the sample gas flow at an interaction reaction. This can be achieved, for example, by using an electric field, a deflector, wings, or a throttle valve (such as a Venturi tube).

[0008] However, these systems correspondingly require a buffer gas or sheath gas at a high pressure typically greater than 100 mbar in the fluid chamber to establish a laminar flow that effectively guides the reagent ions and analytes. This in turn requires the use of high-purity gas or specific cleaning measures to avoid, for example, the formation of unwanted ion species with impurities. In addition, the high pressure in the ion molecule reactor will correspondingly result in a memory effect or a long recovery time of the chamber. Additionally, additional measures are required to provide a buffer gas with a desired constant pressure or to establish a well-defined laminar flow.

[0009] Another concept is disclosed in US2008 / 0217528 A1 (TOFWERK AG), which particularly describes an ion molecule reactor in which reagent ions are generated in a high-pressure reagent ion source and then the reagent ions are fed axially into an elongated chamber that includes a cylindrical rod-shaped electrode as an ion guide. Analyte molecules enter the ion molecule reactor through a side sample inlet and are then ionized by reacting with the reagent ions at an intersection point between the reagent ions and the analyte at the first end of the chamber.

[0010] However, only a limited analyte ion yield and limited sensitivity can be achieved with this apparatus, especially due to the relatively short interaction time between the reagent ions and the analyte.

[0011] Therefore, especially when referring to screening applications of complex mixtures, it is difficult to meet the industrial requirements regarding sensitivity, selectivity, and sample throughput with known techniques.

[0012] For example, in the wine industry, it is desirable to screen corks to reduce spoilage of wine due to contaminants present in the cork (which cause "cork taint"). "Cork taint" is a broad term that describes wine having an undesirable odor or taste, especially spoilage that can only be detected after bottling, aging, and opening. However, screening cork is a challenge due to the extremely low concentration of contaminants to be detected and the complex mixture of VOCs (volatile organic compounds) emitted from cork and wood materials.

[0013] Halophenols or haloanisoles are a class of such contaminants. Thus, 2,4,6-trichloroanisole (TCA) is the most common contaminant, which, when present in higher amounts, makes the wine smell musty or moldy, like cardboard, damp cement, or wet newspaper. In the worst cases, the wine is undrinkable. TCA contamination is not harmful to human health; however, it causes serious problems for wine sealed with cork because it affects the quality and price of the wine.

[0014] When cork is made into stoppers, TCA originates from the chemical processing of cork raw materials. TCA is formed when a specific fungus is treated with chlorinated phenolic compounds, which are an antibacterial agent used in wood processing. Since humans can perceive TCA at extremely low concentrations (ng / L), very small amounts of this compound (about nanograms per liter) may be the cause of this defect.

[0015] Therefore, it is desirable to have an effective and preferably automated screening of cork for haloanisoles such as TCA to prevent spoilage of wine during storage and fermentation.

[0016] US 9,588,089 B2 (Cevaque Invest) describes a method for analyzing cork by gas chromatography (GC). However, this method is slow if sufficient separation is to be achieved to reduce the number of false positives.

[0017] Therefore, there is still a need for further improved techniques and instruments for chemical ionization of analytes, which are particularly suitable for mass spectrometry. In addition, solutions for industrial screening applications involving complex mixtures are needed. SUMMARY OF THE INVENTION

[0018] The object of the present invention is to provide improved devices and methods belonging to the initially mentioned technical field. In particular, improved devices and methods will be provided for detecting and analyzing analytes with high sensitivity and allowing a high sample throughput. In particular, the device and method are adapted to detect cork taints and / or halobenzenes with higher sensitivity and especially sufficient specificity or resolution to reduce the false positive rate. In particular, improved techniques and instruments for the chemical ionization of analytes will be provided, which are particularly suitable for use in mass spectrometry. Thereby, it is desired to obtain the highest possible analyte ion yield. Devices and methods should also be provided which can increase the sensitivity in mass spectrometry and / or allow the measurement of analytes at ultra-low concentrations (e.g., concentrations in the range of a few ppqv (parts per quadrillion by volume) in atmospheric science or the wine industry, etc.). In addition, the techniques and instruments should be as safe and easy to use as possible.

[0019] The solution according to the invention is in particular defined by the features of claim 1. Thus, according to the invention, an ion-molecule reactor for generating analyte ions from an analyte, in particular for use with a mass analyzer and / or for use in mass spectrometry, comprises:

[0020] a) a reaction volume in which reagent ions can interact with the analyte to form analyte ions, in particular by chemical ionization;

[0021] b) at least one analyte inlet which allows the analyte to be introduced into the reaction volume along an inlet path, whereby preferably the direction of the inlet path extends substantially along the direction of at least a first part of a predetermined transport path in the reaction volume;

[0022] c) at least one reagent ion source and / or at least one reagent ion inlet which allows reagent ions to be provided into the reaction volume;

[0023] d) optionally, at least one ion guide which comprises an electrode assembly configured to generate an alternating electric field, magnetic field and / or electromagnetic field which allows at least reagent ions and / or analyte ions to be guided through the reaction volume along at least a part of the predetermined transport path, in particular along the first part of the transport path, preferably along the entire transport path.

[0024] Herein, the term "ion guide" represents a device for altering the velocity of ions with an alternating electric field, magnetic field and / or electromagnetic field. Preferably, the frequency of the alternating electric field, magnetic field and / or electromagnetic field is from about 0.01 - 100 MHz, in particular 0.1 - 10 MHz, especially 0.5 - 5 MHz.

[0025] However, if desired, one or more DC fields can also be applied in addition to the alternating electric, magnetic, and / or electromagnetic fields.

[0026] The ion guide (if present) is configured to selectively change the velocity of ions, in particular without affecting the velocity of neutrals. Thus, the term "velocity" should be understood as a vector having a direction and a magnitude. Accordingly, when the velocity is changed, the direction and / or magnitude of the corresponding ion is changed. In particular, with an ion guide, ions can be accelerated and / or decelerated and / or the direction of movement can be changed. Thereby, the ion guide allows the analyte ions and / or reagent ions to be guided and / or concentrated along a transport path within the reaction volume. In particular, the ion guide provides an ion channel for the analyte ions. Thus, in particular, the ion channel substantially corresponds to the transport path.

[0027] The "reaction volume" is the volume in the space within the ion-molecule reactor where the analyte is ionized by collision with reagent ions. In particular, the reaction volume is correspondingly such a volume where the ion guide is effective or where ions are effectively guided. In particular, the reaction volume is at least partially enclosed in a housing and / or a tubular element. In particular, the housing is a tubular element.

[0028] The term "predetermined transport path" represents the path along which analyte ions are guided through the reaction volume and / or the path along which the analyte ions are expected to move. The transport path can be, for example, a curve, a straight line, or a line having one or more straight portions and / or one or more curved portions. Preferably, with respect to the expected direction of movement of the analyte, at least a first portion of the predetermined transport path extends along a straight line. In particular, the length of the first portion (preferably straight) is at least 5%, preferably at least 10%, in particular at least 25%, advantageously at least 50%, particularly preferably at least 75% of the length of the entire transport path through the reaction volume. In particular, the transport path extends along the central axis and / or the longitudinal axis of the reaction volume and / or the ion-molecule reactor.

[0029] The "analyte inlet" particularly includes a hollow tubular inlet, in particular a cylindrical tube. Thereby, the analyte can be guided through the tubular inlet into the ion-molecule reactor and / or the reaction volume. Preferably, the analyte inlet and / or the analyte inlet path extends parallel or coaxially to the longitudinal axis of the ion guide and / or the ion-molecule reactor.

[0030] The "inlet path" is the path along which the analyte is introduced into the reaction volume and / or the ion-molecule reactor. In particular, the inlet path is substantially straight. Preferably, the inlet path extends substantially perpendicular to the inlet opening or inlet orifice of the analyte inlet, and / or the inlet path extends along the longitudinal axis of the tubular end of the analyte inlet. Thus, the tubular end of the analyte inlet terminates within the ion-molecule reactor.

[0031] Surprisingly, it has been found that the device of the present invention allows for the specific guidance and concentration of reagent ions within the reaction volume, and enables a high density of reagent ions to be achieved in an extended portion of the reaction volume, where the reagent ions can interact with the analyte. Thus, the spatial distribution of the reagent ions can be very effectively controlled with the device of the present invention. Additionally, analyte ions can be guided through the reaction volume along a predetermined transport path.

[0032] Furthermore, the introduction of the analyte into the reaction volume in the direction of at least a first portion of a predetermined transport path through the reaction volume according to the present invention also results in a high density of the analyte in the reaction volume. At the same time, the density of unnecessary and lost analyte outside the reaction volume can be kept at a low level. Thus, with the device of the present invention, a relatively high density of both reagent ions and analyte can be obtained in the reaction volume. Due to the increased likelihood of collision with the reagent ions, this in turn allows for very efficient chemical ionization of the analyte.

[0033] This is in strong contrast, for example, to a device that introduces an analyte into an ion-molecule reactor in a direction substantially perpendicular to a predetermined transport path, such as according to US2008 / 0217528 A1, where substantially all of the analyte that is not immediately ionized at the intersection point with the reagent ions will be lost. Thus, in such a device, there is only a very limited interaction volume between the reagent ions and the analyte.

[0034] With the device of the present invention, for example, a specific analyte in a highly complex mixture can be detected, the mixture containing the analyte at a concentration of 100 ppt or less, particularly 1 ppt or less, especially 0.1 ppt or less, for example 0.01 ppt or less, and particularly 0.001 ppt or less. Thus, the device of the present invention can be used for the direct analysis of complex samples, such as volatile organic compounds evaporated from a cork, without further separation or concentration of the target analyte.

[0035] Moreover, due to the device of the present invention, the reagent ions can be retained within the reaction volume for a longer time, which further correspondingly increases the likelihood of collision with the analyte or the ionization efficiency of the analyte. Additionally, the analyte ions generated by collision with the reagent ions can be guided through the reaction volume by an ion guide along a predetermined path. Thus, the loss of reagent ions or analyte ions due to collision with other atoms or molecules present in the ion-molecule reactor or with elements of the ion-molecule reactor (such as walls, etc.) can be greatly reduced.

[0036] It has been found that the functional and synergistic interaction between the particular way of introducing the analyte into the reaction volume and a particular ion guide (if present) greatly enhances the efficiency of chemical ionization and allows the ionized analyte to be provided in surprisingly high yields.

[0037] Accordingly, the ion-molecule reactor can be operated at pressures far below 10 mbar. This can significantly reduce the problems of unwanted impurities and analyte ion losses due to high rates of collisions with non-analyte gases associated with systems using high-pressure buffer or sheath gases.

[0038] In addition, with the device of the present invention, analyte ions as well as primary ions can be effectively guided along a well-defined path in the reaction chamber space. This allows the ions to be kept away from the walls of the ion-molecule reactor, which results in a low adsorption rate of ions on the walls of the ion-molecule reactor. Accordingly, the amount of ions or molecules desorbing later from the walls of the ion-molecule reactor will also be at a low level. Overall, this results in a reduced memory effect.

[0039] The reduced memory effect in turn leads to a reduction in the recovery time of the ion-molecule reactor, such that the reactor can be used again more quickly after a measurement. In addition, if the ion-molecule reactor is used, for example, in time-resolved measurements of different analyte concentrations, the time resolution of the measurement can be significantly improved. Thus, if different analyte concentrations are to be measured, the small amount of unwanted and previously adsorbed analyte ions or molecules desorbing from the walls of the ion-molecule reactor back into the reaction volume or the transport path will ensure a minimal impact on the actual analyte concentration. Accordingly, the fluctuations in analyte concentration can be measured with a correspondingly higher precision or higher time resolution.

[0040] If the walls of the ion-molecule reactor further comprise at least one porous and / or gas-permeable portion, ions and neutrals reaching the walls of the ion-molecule reactor can also be at least partially removed from the walls, for example by pumping. This will also reduce the amount of unwanted ions or molecules desorbing from the walls of the ion-molecule reactor back into the reaction volume, thereby reducing the memory effect. More details regarding embodiments including porous and / or gas-permeable portions in the walls of the ion-molecule reactor are given below.

[0041] In particular, with the ion-molecule reactor of the present invention, especially in a proton transfer reaction-based chemical ionization system, the sensitivity of mass spectrometry can be increased by at least one order of magnitude.

[0042] Preferably, the reagent ion source and / or the reagent ion inlet are positioned radially outward with respect to a first portion of the predetermined transport path and / or the inlet path. This allows for a highly compact device and efficient introduction of reagent ions into the reaction volume. However, other arrangements may also be suitable.

[0043] In particular, at least one reagent ion source and / or at least one reagent ion inlet is preferably configured such that reagent ions can be introduced into the reaction volume along at least two different directions and / or from at least two different positions. The at least two different directions are in particular non-parallel directions, preferably both intersecting the inlet path and / or the first part of the transport path. The at least two different positions are two positions separated in space. Preferably, the at least two different positions are located in at least two different radial directions with respect to the inlet path and / or the analyte inlet. Thereby, the at least two different radial directions extend substantially perpendicular to the direction of the inlet path and / or the analyte inlet. In particular, the at least two different positions are included in a sector-shaped region or an annular region surrounding the inlet path and / or the analyte inlet. In particular, the angle between the two radial directions in which the two furthest positions of the at least two different positions are located is at least 2°, such as at least 5°, in particular at least 10°, in particular at least 22.5°, such as at least 30°, advantageously at least 45°, in particular at least 45°, particularly preferably at least 60°, such as at least 90°, at least 120° or at least 180°. Between the two furthest positions, any number of other positions may be present.

[0044] If there are multiple reagent ion sources and / or analyte inlets, then preferably all reagent ion sources and inlets are configured such that reagent ions can be introduced into the reaction volume along at least two different directions and / or from at least two different positions.

[0045] Surprisingly, it has been found that such a device allows for even more efficient provision of reagent ions and their introduction into the reaction volume. When reagent ions are introduced into the reaction volume along at least two different directions and / or from at least two different positions, the reagent ions can be specifically directed and concentrated towards the reaction volume, and the density of the reagent ions in the extended part of the reaction volume can be further increased. Thus, the spatial distribution of the reagent ions can be very precisely controlled using such a device. Specifically, such a device will further reduce the tendency of the reagent ions to deviate and collide with the walls when entering the reaction volume.

[0046] However, for specific applications, other arrangements may also be beneficial, for example.

[0047] The ion-molecule reactor may include at least one reagent ion source, which may be installed inside and / or outside the ion-molecule reactor. Moreover, different reagent ion sources may be present inside and / or outside the ion-molecule reactor simultaneously. Instead of or in addition to at least one reagent ion source, the ion-molecule reactor may include at least one reagent ion inlet. In this case, the reagent ions may be generated, for example, by an external reagent ion source and then guided through the reagent ion inlet into the ion-molecule reactor. The reagent ion inlet may be, for example, a tubular inlet, optionally having an element for guiding the reagent ions. Preferably, the ion source is configured to generate a total beam of reagent ions and to direct and / or focus the total beam of reagent ions towards the reaction volume.

[0048] In particular, at least one reagent ion source and / or at least one reagent ion inlet are configured to generate one or more beams of reagent ions, the inlet direction extending at an angle of 0 - 100°, in particular 5 - 100°, especially 45 - 95°, for example 60 - 90° or substantially orthogonally to the direction of the inlet path and / or the first part of the transport path. However, especially in combination with the beams of reagent ions that are, for example, ring-sector-shaped, annular, or disk-shaped as described below, the one or more beams of reagent ions preferably extend at an angle of 0 - 10°, more preferably 0 - 5°, and most preferably 0° to the direction of the inlet path and / or the first part of the transport path.

[0049] With such a device, the reagent ions can be directly directed and / or focused into the reaction volume or the first part of the transport path. This will result in a high concentration of reagent ions in the reaction volume.

[0050] However, reagent ion sources and / or ion inlets with other properties may also be used.

[0051] Preferably, at least one reagent ion source and / or at least one reagent ion inlet are configured to generate a total beam of reagent ions having rotational symmetry or circular symmetry. In other words, in this case the total beam of reagent ions is axially symmetric. Thereby, the symmetry is preferably given with respect to an axis defined by the direction of the first part of the transport path, the analyte inlet, and / or the inlet path. The rotational symmetry may be, for example, n-fold symmetry, where n ≥ 2. If n → ∞, circular symmetry is given. The "total beam" means the sum or superposition of all partial beams originating from at least one reagent ion source and / or at least one reagent ion inlet or together from all reagent ion sources and all reagent gas inlets. Thereby, the reagent ions are introduced into the reaction volume along at least two different directions and / or from at least two different positions.

[0052] It has been shown that such symmetric beams of reagent ions are very beneficial for obtaining a high density of reagent ions with a substantially uniform distribution in the reaction volume.

[0053] However, for a specific application, for example, a reagent ion source with a total beam without rotational symmetry or circular symmetry can also be used.

[0054] In particular, the reagent ion source is configured to generate a generally toroidal, annular, disk-shaped, and / or conical beam of reagent ions, especially an annular beam of reagent ions. Thus, preferably, the beam is axially symmetric about an axis defined by the direction of the first part of the transport path, the analyte inlet, and / or the inlet path. In particular, the conical beam can have the form of a conical surface or a conical volume.

[0055] In an annular or disk-shaped beam, the reagent ions correspondingly move particularly longitudinally from the outer periphery towards the central longitudinal axis of the annulus or disk.

[0056] In the case of a conical beam, the reagent ions move especially from the base towards the apex of the cone. Additionally, the conical beam (if present) is preferably oriented such that the apex of the conical beam points towards the reaction volume, especially on the first part of the transport path.

[0057] In any case, with such an ion beam, in principle, the reagent ions can be introduced into the reaction volume in countless different directions and / or from countless different positions. This allows for a further increase in the density and uniformity of the reagent ions in the reaction volume. This, in turn, will improve the efficiency of the ionization reaction in the reaction volume and increase the yield of analyte ions.

[0058] Particularly preferably, at least one reagent ion source and / or at least one reagent ion inlet is annular and / or has the shape of one or more annular sectors. Preferably, at least one reagent ion source and / or at least one reagent ion inlet is arranged coaxially around the first part of the transport path, the inlet path, and / or the analyte inlet. Particularly preferably, the ion-molecule reactor includes exactly one annular reagent ion source or exactly one annular reagent ion inlet.

[0059] With such a device, an axially symmetric beam of reagent ions with a highly uniform distribution can be particularly generated. Additionally, with an annular and / or a reagent ion source and / or reagent ion inlet having the shape of one or more annular sectors, the reagent ions can be introduced into the reaction volume in at least two different directions and / or from at least two different positions in a simple and reliable manner.

[0060] According to another advantageous embodiment, the ion-molecule reactor includes at least two, especially at least three, four, five, six, seven, or even more individual reagent ion sources and / or reagent ion inlets, which are preferably arranged on a circular line around the first part of the transport path, the inlet path, and / or the analyte inlet, whereby preferably the circular line is concentric with the first part of the transport path, the inlet path, and / or the analyte inlet.

[0061] In particular, if present, at least two separate reagent ion sources and / or at least two separate reagent ion inlets are arranged symmetrically around a first part of the transport path, the inlet path, and / or the analyte inlet.

[0062] Using at least two separate reagent ion sources and / or reagent ion inlets, the splitting of reagent ions from the two sources and / or inlets can be flexibly controlled, and the split beams can then be independently introduced into the reaction volume along at least two different directions and / or from at least two different positions. However, a high density and uniform distribution of reagent ions can still be obtained in the reaction volume. This is especially true with a symmetrical arrangement.

[0063] In particular, at least one reagent ion source and / or at least one reagent ion inlet includes an annular nozzle and / or an annulus-sector nozzle. In particular, these nozzles have at least one annular and / or slit-shaped opening. Several openings can also be arranged in an annular manner, such as circular and / or elongated openings.

[0064] This type of nozzle also allows for the reliable generation of an axially symmetric beam of highly uniform reagent ions.

[0065] However, for example, instead of or in addition to the annular and / or annulus-sector nozzles, other nozzles can also be used. For example, at least one reagent ion source and / or at least one reagent ion inlet can have two separate tubular nozzles.

[0066] According to another preferred embodiment, at least one reagent ion source and / or at least one reagent ion inlet includes at least one guiding element for guiding the reagent ions before they enter the reaction volume. Thus, the guiding element is different from an ion guide, which is used to guide reagent ions and / or analyte ions through at least a part of a predetermined transport path through the reaction volume. Specifically, in the direction of movement of the reagent ions, the guiding element is located in front of the reaction volume.

[0067] Preferably, the guiding element is configured to generate an electric field, a magnetic field, and / or an electromagnetic field, which allows the reagent ions to be guided before they enter the reaction volume, in particular by concentrating, accelerating, and / or decelerating the reagent ions. By doing so, the reagent ions can be flexibly and highly accurately guided into the reaction volume with a predetermined energy and / or speed. This further increases the ionization rate of the analyte in the reaction volume, and thus increases the total yield of analyte ions generated in the ion-molecule reactor. In addition, when changing from one reagent gas to another, the guiding element of at least one reaction ion source and / or at least one reaction ion inlet allows for the compensation of the different properties of the reagent gases in a very easy and effective manner without changing the mechanical equipment.

[0068] In particular, if present, the guiding element of at least one reagent ion source and / or at least one reagent ion inlet comprises an electrode assembly, preferably comprising at least two electrodes. For example, the guiding element comprises a multipole electrode assembly, an ion funnel and / or an ion carpet. The electrode assembly, multipole electrode assembly, ion funnel and / or ion carpet of the guiding element may be similar to the multipole electrode assembly, ion funnel and / or ion carpet described below in connection with the ion guide.

[0069] However, the guiding element of at least one reagent ion source and / or at least one reagent ion inlet is only optional and may be omitted.

[0070] If present, at least one reagent ion source is preferably selected from a discharge-based reagent ion source, a plasma-based reagent ion source, a photoionization-based reagent ion source, an x-ray reagent ion source and / or a radioactive reagent ion source. For example, the reagent ion source is a glow discharge-based reagent ion source, a radio frequency-based reagent ion source, a microwave-based reagent ion source, a corona discharge-based reagent ion source and / or a dielectric barrier glow discharge-based reagent ion source.

[0071] Such reagent ion sources are in principle known to those skilled in the art and allow good controllable ionization of the reagent gas to form specific reagent ions. However, for specific applications, it may be beneficial to use other reagent ion sources.

[0072] Preferably, the reagent ions used in the present invention are positively charged ions, such as H 3 O + 、O 2 + 、CH 4 + 、NH 4 + 、isobutane ions and / or NO + . Thus, the ion source is particularly capable of generating such ions. However, other reagent ions, including negatively charged ions, may also be suitable.

[0073] Particularly preferably, H 3 O + as the reagent ions in the present invention. This allows the generation of analyte ions by proton transfer reaction (PTR), which is very beneficial for the analysis of volatile organic compounds (VOCs).

[0074] However, for the analysis of halogenated anisoles, such as TCA, positively charged reagent ions, such as O 2 + and / or NO + , especially NO + are particularly preferred.

[0075] The ion guide particularly includes an electrode assembly having at least two, particularly at least three, particularly at least four, preferably at least five, particularly at least six or at least eight electrodes, for generating an alternating electric field, magnetic field, and / or electromagnetic field to guide, concentrate, accelerate, and / or decelerate ions, particularly analyte ions and reagent ions, within a reaction volume and / or along a predetermined transport path. In particular, the ion guide may include an electrode assembly having exactly two, three, four, five, six, or eight electrodes. The electrodes are particularly selected from conductive rods, ring electrodes, coatings, and / or stripes.

[0076] In particular, the electrode assembly is configured to generate a guiding field for guiding and / or concentrating ions, particularly analyte ions and / or reagent ions, along the transport path. The guiding field is preferably an electromagnetic field, particularly a radio frequency (RF) field, which generates an effective electric potential that confines the ions to a region along the transport path. Such a guiding field greatly helps to concentrate the ions in the reaction volume and prevent the ions from hitting the walls of the ion-molecule reactor. This in turn will greatly improve the overall yield of analyte ions.

[0077] Preferably, the electrode assembly is configured to generate a transport field for accelerating and / or decelerating ions in the direction along the transport path. With such a transport field, for example, the reaction time between reagent ions and the analyte can be controlled very precisely. In particular, the transport field is an electric field, especially a DC field, which extends substantially along the transport path. However, the first field can also be a superposition of electromagnetic fields.

[0078] In particular, the electrode assembly is configured to generate a rotating field. Preferably, the rotating field causes ion motion that traces a path around the average flight path of the ions. This particularly allows setting a constant energy for the ions. Possible embodiments of such an electrode assembly in a multipole assembly are described below. However, other embodiments may also be suitable.

[0079] Most preferably, the ion guide includes an electrode assembly configured to generate a transport field independently of the guiding field. Even more preferably, the ion guide includes an electrode assembly additionally configured to generate a rotating field. With such a device, the speed of ions along a predetermined path can be controlled in an efficient manner independently of the concentration and / or guiding of the ions.

[0080] However, alternatively or additionally, other components for guiding neutrals and / or ions can also be used.

[0081] In particular, the ion-molecule reactor includes at least one voltage generator, which can be electrically connected to the ion guide or the electrode assembly of the ion guide or at least two electrodes accordingly. In particular, at least one voltage generator is capable of providing an alternating voltage and optionally additionally providing a direct current voltage. Preferably, there are at least two voltage generators or at least one voltage generator having at least two separately controllable outputs, whereby the first voltage generator or the first output can be connected to the first electrode accordingly, while the second voltage generator or the second output can be connected to the second electrode accordingly. Thus, each electrode can be used to separately generate an electric field and / or an electromagnetic field.

[0082] In particular, if there is at least one reagent ion source and / or a guiding element of at least one ion inlet, the ion-molecule reactor includes at least one additional voltage generator that can be electrically connected to the guiding element.

[0083] Preferably, the ion guide includes a multipole electrode assembly, an ion funnel, and / or an ion blanket.

[0084] The ion funnel can include, for example, a stack of at least two electrodes, especially a stack of annular electrodes with a gradually decreasing inner diameter. Preferably, the ion funnel includes at least three, four, five, or even more electrodes. In particular, the annular electrodes are arranged coaxially with respect to at least a first portion of the analyte inlet and / or a predetermined transport path in the reaction volume, or the longitudinal axis of the ion funnel is arranged coaxially with respect to at least a first portion of the analyte inlet and / or a predetermined transport path in the reaction volume.

[0085] The ion funnel is preferably configured such that reagent ions and / or analyte ions are radially restricted when passing through the ion funnel during operation. In particular, during operation, a heterogeneous alternating potential, such as a radio frequency potential, can be applied to adjacent electrodes. In other words, the phase of the voltage alternates between the electrodes. Additionally, a direct current voltage gradient (DC gradient) can be applied in the longitudinal axis direction of the ion funnel to accelerate and / or decelerate the ions.

[0086] The ion blanket preferably includes a substantially planar arrangement of at least two electrodes, preferably a plurality of electrodes (such as points, strips, and / or rings), to each of which a different voltage can be applied. The electrodes themselves can be arranged in a radial pattern and / or a linear array. According to a very advantageous embodiment, the electrodes include at least two or more separate concentric rings.

[0087] In particular, the electrodes surround the orifice in the ion blanket. Thus, in operation, a voltage is applied to the electrodes of the ion blanket, thereby generating an alternating electric field that causes reagent ions and / or analyte ions to converge through the orifice. Sometimes, the ion blanket is also referred to as a planar ion funnel. Highly advantageous embodiments of planar ion funnels and their operation are described in US2013 / 0120897 A1 (Amerom et al.).

[0088] Particularly preferably, the ion guide comprises a multipole electrode assembly, such as a quadrupole and / or octupole electrode assembly. The multipole electrode assembly preferably comprises elongated electrodes arranged along and / or around the transport path. In this case, preferably, the transport path extends along a longitudinal multipole axis (e.g., along a quadrupole axis).

[0089] Such an assembly is particularly preferred for generating a guiding field for guiding and / or focusing ions along the transport path. It is well known that an oscillating inhomogeneous electric field forms a so-called effective potential that is proportional to E 2 where E is the amplitude of the oscillation of the electric field strength (see, for example, Landau L.D., Lifshitz E.M.: Mechanics, Pergamon Press, Oxford, 1976; Gerlich, D. “Inhomogeneous Electrical Radio Frequency Fields: A Versatile Tool for the Study of Processes with Slow Ions”, in State-Selected and State-to-State Ion-Molecule Reaction Dynamics, edited by C.Y. Ng and M. Baer, Advances in Chemical Physics Series, LXXXIL 1, 1992). In the case of a quadrupole RF electric field, the effective potential results in a net force on the ions towards the quadrupole axis. This force is inversely proportional to the ion mass-to-charge ratio (m / Q) and proportional to the distance of the ion from the quadrupole axis. This fundamental property of the effective potential causes ions with a given m / Q to oscillate slowly around the quadrupole axis, with a characteristic frequency inversely proportional to their m / Q, i.e., the quadrupole field and similarly higher multipole fields are confinement fields suitable for guiding and focusing analyte ions and / or reagent ions according to the present invention.

[0090] Parabolic or circular coaxial rods are typically used to generate a linear RF multipole field that is particularly adapted to the ion guide of the present invention. Other shapes can be used, for example, to approximate a quadrupole field. Preferably, a primary pure RF field is applied between a set of opposing electrodes or rods.

[0091] In a particularly preferred embodiment, a rotating multipole field, in particular a rotating quadrupole field, is generated at at least one electrode. In principle, the utilization of such fields is known, for example from fundamental kinetic studies (see V.V. Raznikov, I.V. Soulimenkov, V.I. Kozlovski, A.R. Pikhtelev, M.O. Raznikova, Th. Horvath, A.A. Kholomeev, Z. Zhou, H. Wollnik, A.F. Dodonov; "Ion rotating motion in a gas-filled radio-frequency quadrupole ion guide as a new technique for structural and kinetic investigations of ions"; Rapid Communications in Mass Spectrometry, Vol. 15, No. 20, pp. 1912 - 1921). When appropriately adjusted, such a rotating field causes ion motion along a trajectory around the mean flight path of the ions. This enables the setting of the ions or energy independently of the focusing field and / or transport field. Furthermore, due to the rotating field, the length of the flight path can be increased, which in turn increases the likelihood of ionization of analyte molecules.

[0092] Further details of suitable electrode assemblies and their operation are given in US Patent Application US2008 / 0217528A1 (Tofwerk AG).

[0093] According to a particular embodiment, the ion guide includes at least two different multipole electrode sections. For example, the ion guide includes a quadrupole section followed by an octupole section. Thus, the first section (e.g., the octupole section) can be adapted or used, for example, to compress reagent ions to increase the ionization reaction with the analyte, while the second section (e.g., the quadrupole section) is used to focus and / or guide the analyte ions along the transport path. Such an assembly will further improve the overall efficiency of the process.

[0094] However, the multipole assembly is optional and can be omitted if not required. More complex multipole assemblies can also be envisaged for specific applications.

[0095] Instead of or in addition to the multipole, for example, an ion funnel and / or an ion blanket as described above can be used. Additionally, any other ion guide including an electrode assembly can be suitable, the electrode assembly being configured to generate an alternating electric field, magnetic field, and / or electromagnetic field, allowing the guiding of reagent ions and / or analyte ions at least along a part of a predetermined transport path, preferably along the entire transport path.

[0096] According to certain embodiments, the ion guide includes a multipole assembly as described above, particularly in combination with an ion funnel and / or an ion blanket as described above. It has been found that such a device even better allows for the specific guidance and concentration of reagent ions within the reaction volume and enables a high density of reagent ions to be achieved in an extended portion of the reaction volume. Thus, the total yield of analyte ions can be further increased.

[0097] In particular, the ion funnel and / or the ion blanket are arranged behind the ion guide in the direction of the transport path. This allows for the specific extraction of analyte ions in a defined direction and for them to leave the reaction volume with a high yield.

[0098] However, such a combination of different ion guiding elements is optional and can be omitted accordingly if not desired or required.

[0099] Preferably, the ion-molecule reactor further includes a tubular element that at least partially, preferably completely, surrounds the reaction volume and / or the transport path. The tubular element is preferably cylindrical, particularly having a circular cross-section. However, a rectangular or square cross-section is also possible. Additionally, a tubular element having at least two different cross-sections can be used. Furthermore, the tubular element can be straight or bent.

[0100] In particular, the length of the tubular element in the longitudinal direction is >10 mm, especially >100 mm, particularly >500 mm, especially >1000 mm, >2000 m, >5000 mm, or >10000 mm. The ratio of the inner diameter to the length of the tubular element can be, for example, between 1:1.5 - 1:5000, particularly between 1:1 - 500, especially between 1:2 - 1:50, particularly between 1:5 to 1:20. The ratio of the wall thickness to the inner diameter of the tubular element can be, for example, between 1:1 - 1:50, particularly between 1:5 - 1:20.

[0101] For example, when made of plastic, the tubular element can be at least partially or completely flexible or bendable. However, a rigid tubular element made of, for example, glass and / or ceramic can also be used. Embodiments with a bendable tube enable, for example, the ion-molecule reactor to be used accordingly as a probe or a probe head, for example for collecting analyte samples at random locations. Thus, ions can be transported over a relatively long distance, for example over several meters. This may be similar to a vacuum cleaner.

[0102] If the ion-molecule reactor includes at least one electrode as described above, the at least one electrode can be arranged inside the tubular element, within the wall of the tubular element, and / or outside the tubular element. Additionally, a coating can be applied to the tubular element, and the coating can be used as an electrode. In a preferred embodiment, the at least one electrode is made of a material having a lower resistivity than the material of the tubular element.

[0103] Particularly preferably, at least one electrode is arranged within the wall of the tubular element and / or outside the tubular element. This particularly helps to reduce contamination of the electrode.

[0104] If at least one electrode is an elongate structure, the at least one electrode can be positioned relative to the tubular element in the longitudinal direction and / or wound around the tubular element. However, other arrangements are also possible.

[0105] In a particular embodiment, the tubular material is made of an electrically insulating material and / or a high-ohmic resistance material, for example made of perfluoroalkoxy polymer (PFA), such as Teflon and / or polytetrafluoroethylene (PTFE). In this case, the tubular element can be used as at least one electrode or as another electrode, in particular as an electrode for generating a transport field, in particular an electric field such as a DC field. However, instead of or in addition to the electrode in the form of a tubular element, an annular electrode can also be used.

[0106] More details of possible arrangements of the tubular element and the electrode are given in US Patent Application US2008 / 0217528 A1 (Tofwerk AG).

[0107] In particular, the tubular element includes at least one porous and / or gas-permeable part, in particular for introducing a fluid into the reaction volume and / or removing neutrals and ions that have left the predetermined transport path from the reaction volume and / or the ion-molecule reactor. In a particular embodiment, the tubular element is porous and / or gas-permeable along its entire length. In particular, the porous and / or gas-permeable part covers at least 5%, in particular at least 25%, especially at least 50% or at least 75% of the surface of the tubular element.

[0108] The at least one porous and / or gas-permeable part can for example include a filter, a mesh and / or a frit. In particular, the at least one porous or gas-permeable part surrounds the reaction volume at least along a local part of the transport path in the reaction volume or along the entire transport path. Preferably, the at least one porous or gas-permeable part is an annular or ring-shaped part of the tubular element.

[0109] The fluid can for example be a sheet gas and / or a buffer gas, which can be introduced into the ion-molecule reactor, in particular in the radial direction, for example to reduce wall effects or memory effects. The fluid can be introduced into the ion-molecule reactor, for example, by being driven by a pressure difference between the internal pressure and the external pressure of the tubular element.

[0110] However, reagent gas and / or reagent ions can also be introduced into the reaction volume, in particular in the radial direction, through at least one porous and / or gas-permeable part of the tubular element. In this case, at least one porous part of the tubular element has the function of a reagent ion inlet. For example, reagent ions can be generated outside the tubular element by a reagent ion source as described above.

[0111] When removing neutrals and ions that have left the predetermined transport path from the reaction volume and / or the ion-molecule reactor through the porous and / or gas-permeable part, the efficiency of the ion-molecule reactor can be further increased, because wall effects and memory effects can be reduced, and the total pressure in the reaction volume can be lowered. Therefore, at the same outlet pressure, a higher analyte ion yield can be obtained.

[0112] Advantageously, in the longitudinal direction, the tubular element has at least one non-porous or airtight first part and a porous or gas-permeable second part. Preferably, the airtight part is oriented towards the analyte inlet, while the gas-permeable part is oriented downstream with respect to the direction of movement of the analyte ions. With this arrangement, the ionization reaction of the analyte with the reagent ions can occur in the airtight part, which is advantageous in terms of the ionization rate of the analyte ions. Further downstream, since the porous or gas-permeable part allows the density of non-ionized analyte and other substances to be reduced, the efficiency of analyte ion transport can be increased.

[0113] According to another preferred embodiment, the tubular element is included within an outer tubular element. In particular, the outer tubular element is airtight or non-porous. For example, the outer tubular element is made of stainless steel.

[0114] In particular, the inner diameter of the outer tubular element is greater than the outer diameter of the tubular element. Thus, in this case, there is a free volume between the tubular element and the outer tubular element. This volume can be used, for example, to provide a fluid, such as a gas, which is introduced into the reaction volume through the porous or gas-permeable part of the tubular element. The pressure in the free volume can also be reduced to a value lower than the pressure in the reaction volume in order to remove neutral analytes and other substances from the reaction volume by means of a pressure difference.

[0115] Preferably, the outer tubular element includes an opening for introducing a fluid and / or for evacuating the free volume between the two tubular elements.

[0116] Preferably, the ion-molecule reactor comprises a housing having a longitudinal axis, in particular an elongated housing, especially a cuboid and / or cylindrical tubular member. Preferably, the housing has an exit orifice for analyte ions. If there is a tubular element and / or an outer tubular element, it may be part of the housing. In particular, the analyte inlet and / or the analyte inlet direction extend parallel or coaxial to the longitudinal axis of the housing and / or the analyte inlet direction is directed towards the exit orifice.

[0117] If the analyte inlet direction is directed towards the exit orifice, the analyte and analyte ions can move, for example, along a substantially straight line through the reaction volume. Thus, a direct transport path can be defined, which can be beneficial for efficiency and analyte ion yield.

[0118] In particular, the ion-molecule reactor comprises a housing having an exit orifice for analyte ions, wherein preferably, the orifice area of the exit orifice is 0.002 - 79 mm 2 、especially 0.03 - 20 mm 2 、especially 0.07 - 7 mm 2 、preferably 0.2 - 3.1 mm 2 、0.4 - 1.8 mm 2 。In particular, the exit orifice is circular, and the aperture of the exit orifice is 0.05 - 10 mm, especially 0.2 - 5 mm, especially 0.3 - 3 mm, preferably 0.5 - 2 mm or 0.7 - 1.5 mm.

[0119] Thus, compared with hitherto known ion-molecule reactors, the orifice area or aperture of the exit orifice can be correspondingly reduced without significant loss of analyte ions. This is attributed to the device of the present invention, which allows the reagent ions and / or analyte ions to be effectively concentrated and guided within a clearly defined and radially narrow region. Therefore, an exit orifice with a relatively small orifice area or aperture can even be used.

[0120] Since the conductivity of the exit orifice (volume flow rate, for example, in liters per second) is proportional to the orifice area, the smaller the orifice area of the exit orifice, the lower the conductivity of the exit orifice. Therefore, in the case of a small orifice area of the exit orifice, less unwanted gas leaves the ion-molecule reactor through the exit orifice and enters the subsequent chamber. This in turn allows a correspondingly smaller pump or a pump with a lower pumping capacity to maintain a predetermined pressure in the subsequent chamber. Using a smaller pump enables a more compact instrument to be realized with the ion-molecule reactor.

[0121] For example, in the case of a circular shape leaving the orifice, the orifice area is proportional to the square of the orifice diameter. Thus, reducing the orifice diameter by a factor of 10 will reduce the orifice area by a factor of 100. Therefore, the orifice diameter is a very effective parameter for controlling the conductivity leaving the orifice and the overall size of the instrument using the ion molecule reactor.

[0122] Preferably, the ion molecule chamber is operated under conditions such that the cross-sectional area of the analyte ion beam reaching the orifice is equal to or less than the orifice area leaving the orifice. Under such conditions, the yield of analyte ions is maximized.

[0123] The ion molecule reactor can be used for mass spectrometry. Accordingly, the present invention also relates to a mass spectrometer comprising the ion molecule reactor as described above.

[0124] The mass spectrometer can for example comprise a time-of-flight mass analyzer, a quadrupole mass analyzer, an ion trap analyzer, a sector field mass analyzer, a Fourier transform ion cyclotron resonance analyzer, an Orbitrap analyzer, especially in the analyzer housing. However, other mass analyzers can also be used.

[0125] Thereby, the ion molecule reactor is particularly connected to the mass analyzer such that the analyte ions generated in the ion molecule reactor can be introduced into the mass analyzer. If desired, a transfer device (e.g., an ion transfer tube) can be arranged between the ion molecule reactor and the mass analyzer. This allows for example to provide one or more intermediate pressure regions between the ion molecule reactor and the mass analyzer. Since the mass analyzer typically operates under high vacuum conditions, such a measure can gradually reduce the pressure.

[0126] Furthermore, additional mass and / or energy filters can be envisaged between the ion molecule reactor and the mass analyzer.

[0127] Advantageously, the ion molecule reactor comprises the housing as described above. With this arrangement, the ion molecule reactor can be easily attached to the various mass analyzers contained in the analyzer housing. However, in principle the ion molecule reactor and the mass analyzer can also be included in the same housing.

[0128] In addition, the present invention relates to a kit or device comprising the ion molecule reactor or mass spectrometer as described above and a sampler for collecting at least one analyte from a sample (especially a solid sample).

[0129] However, it should be noted that the sampler for collecting at least one analyte from a sample can be used independently of the other components, kits, devices or equipment of the ion molecule reactor described herein. For example, the sampler for collecting at least one analyte from a sample can be used in combination with chromatography or extraction.

[0130] In particular, the sampler is a headspace sampler and particularly includes a hollow body, in particular a container, a bottle, a syringe and / or a hollow tube.

[0131] The sampler can be configured to be airtight, or the sampler can be configured as a non-airtight closed device.

[0132] According to a preferred embodiment, the sampler includes a heatable container for receiving a sample, an inlet for introducing a gaseous fluid into the interior of the container, and an outlet for recovering the gaseous fluid from the sampler.

[0133] In particular, the container includes an opening for inserting a sample, in particular a cork, into the container.

[0134] Thus, preferably, the edge of the opening is configured to encapsulate the sample in a given contact area when the sample is placed in the container. With such a container, for example, a sample, such as a cork, can be used to close the container. Thus, in this case, no additional closure is required, which may be advantageous for automated screening applications. However, other configurations are also possible.

[0135] For example, the container can also have a stopper and / or a movable closure, such as a plunger and / or a piston, which allows the container and / or the opening to be closed. In this case, the container can be, for example, a syringe-type container and / or a syringe.

[0136] With a movable closure, for example, an analyte extracted from the sample can be pushed out of the container. Additionally, a sample, such as a cork, can be placed in the container, the container is closed with a movable closure, and can optionally be pre-filled with a carrier gas so that the analyte extracted from the sample (preferably by evaporation) accumulates in the container and is then introduced into an ion-molecule reactor. Subsequently, the fluid (especially a gaseous fluid) surrounding the cork and including the extracted analyte can be pushed out of the container through the movable closure (such as a plunger and / or a piston). This allows the extraction of the sample fluid without further dilution and maintains a defined flow rate and / or pressure.

[0137] According to another preferred embodiment, the container and / or the opening are configured such that there is a free passage between the container and / or the opening when the sample is placed in the container and / or when the container is placed above the sample. In this case, preferably, the free passage can be used as an overpressure relief port, for example.

[0138] Furthermore, in particular, the container and / or the opening are configured such that they do not contact the sample, especially the cork, when the sample is placed in the container and / or when the container is placed above the sample. For example, the container can be a single-ended closed tubular container having a free opening on the opposite side. In such an embodiment, preferably, the opening is larger than the sample to be introduced. With this device, the container does not contact the sample being analyzed, especially the cork. Thus, residue and / or memory effects in the container from one sample to the next can be prevented.

[0139] Preferably, the sampler includes a heating element that allows heating of the container, especially to a temperature of 20 - 300 °C, preferably 30 - 100 °C, especially 40 - 75 °C. The heating element can be an integrated heating element, which is, for example, integrated in the container. Additionally or alternatively, an external heating element can be used. Preferably, the external heating element can be connected to and separated from the container through a mechanical interface. For example, the heating element includes or consists of a heating wire, an induction heater, a microwave source, and / or an infrared source.

[0140] With the heating element, the sample in the sampler can be heated, causing the analyte contained in the sample to evaporate. However, evaporation of the analyte can also be achieved without a heating element, for example, by reducing the pressure in the sampler.

[0141] Particularly preferably, the sampler includes a heat exchanger element for preheating the gaseous fluid before it enters the inlet. Thus, preferably, the heat exchanger element allows the gaseous fluid to contact the outer surface of the container before it enters the inlet. In this case, if the container is heated to a certain temperature, the gaseous fluid can be heated to the temperature of the container in an effective and reliable manner.

[0142] If the sampler includes a container, the container preferably includes or consists of a single-ended closed tubular container, especially having an outlet in the end face of the single-ended closed tubular container and / or an inlet in the side of the single-ended closed tubular container. Preferably, the inlet is located in the region of the open end of the single-ended closed tubular container. Preferably, the tubular container is cylindrical, especially toroidal cylindrical. However, the container can in principle be of any shape. For example, the container can have a prismatic shape, for example, with a triangular or rectangular base.

[0143] The inlet is preferably an annular or annular segment-shaped slit in the side of the single-ended closed tubular container. The outlet is especially a central hole in the closed end face of the container.

[0144] With such an embodiment, it is possible to easily introduce a sample through the open end of a single-ended closed tubular container, with the inlet and outlet being maximally spaced apart. In summary, such a configuration helps to optimally mix the analyte evaporated from the sample in the container with a gaseous fluid (e.g., a carrier gas), which is introduced via the inlet before leaving the container via the outlet.

[0145] In particular, the single-ended closed tubular container is included within a spaced tubular housing such that there is a closed and free volume around the sides of the single-ended closed tubular container, and preferably such that the open end of the single-ended closed tubular container remains freely accessible from the outside.

[0146] In particular, the spaced tubular housing includes an opening for introducing the gaseous fluid from outside the sampler into the free volume around the sides of the single-ended closed tubular container.

[0147] Therefore, preferably, the inlet for introducing the gaseous fluid into the interior of the container is in communication with the free volume around the sides of the single-ended closed tubular container.

[0148] With the spaced tubular housing, it is possible to preheat the gaseous fluid via the container in a very effective manner before it enters the inlet without the need for an additional heating stage. Thus, such a configuration represents a very beneficial heat exchanger.

[0149] However, for example, a gaseous fluid that has been preheated with an external heating stage can be provided.

[0150] Preferably, the container includes an overpressure relief port, a breathable part, and / or a breathable closure. The breathable part and / or the breathable closure can be made of, for example, fritted glass and / or sintered metal. Additionally, the breathable part and / or the breathable closure can be a perforated area or plate.

[0151] In particular, the overpressure relief port, the breathable part, and / or the breathable closure allow for stable fluid communication between the interior of the container and the outside of the sampler.

[0152] With the overpressure relief port, the breathable part, and / or the breathable closure, it is possible to collect the analyte from the sample and / or the heating operation under constant pressure conditions and / or undefined non-airtight conditions. This can be beneficial for the rate at which the analyte evaporates from the sample.

[0153] However, alternatively, the overpressure relief port can be omitted. In this case, the analyte can be collected from the sample and / or the heating operation under airtight sealing conditions.

[0154] In particular, the breathable part and / or the closure is an annular element or an annular segment element. Therefore, preferably, the inner diameter of the annular element or the annular segment element is smaller than the inner diameter of the container.

[0155] Preferably, a breathable part and / or a closure, in particular an annular element or an annular segment element, is placed inside the inlet. In a particular embodiment, the breathable part and / or the closure projects into the container interior from the inlet. In particular, if present, the glass frit ring is arranged concentrically with respect to the longitudinal axis of the container.

[0156] An annular element or an annular segment element, in particular if it projects into the container interior from the inlet, can be used as a fixture for the sample, in particular if the sample is a cork. Thus, the annular element or the annular segment element can be configured to hold a part of the sample in a defined position in the container, for example by clamping.

[0157] Preferably, the sampler comprises a part for holding the sample and / or a part for releasing the sample from the sampler. As described above, this can be achieved, for example, using an annular element or an annular segment element. However, other parts such as mechanical clamps, fasteners, locks, etc. can also be envisaged.

[0158] According to another preferred embodiment, the kit or device further comprises a sampling unit, in particular an automatic sampling unit, which is capable of loading a plurality of samples into the sampler in sequence. Preferably, a first sample can be loaded into the sampler, and then at least one analyte can be collected from the first sample. Subsequently, at least one analyte is introduced into the reaction volume of the ion-molecule reactor. The first sample is unloaded from the sampler, and then the next sample is loaded into the sampler, and so on.

[0159] Such a sampling unit is particularly beneficial for industrial screening applications (such as cork screening). However, if high throughput is not an issue or for other purposes, it may be sufficient to manually load the sample into the sampler without a sampling unit.

[0160] In particular, the sampling unit comprises a conveyor, such as a conveyor belt; a manipulator for placing the sampler above the sample; and / or a manipulator for loading the sample into the sampler.

[0161] According to another advantageous embodiment, the kit or device comprises a plurality of samplers, in particular a plurality of samplers as described above. In this case, a plurality of samples can be loaded into the plurality of samplers in parallel, and the analytes collected in each of the plurality of samplers are introduced into the reaction volume of the ion-molecule reactor sequentially or simultaneously.

[0162] Thus, preferably, the kit or device comprises a multi-port valve having a plurality of valve inlets, whereby each valve inlet can be connected to a separate sampler; and one or more valve outlets, whereby at least one valve outlet can be connected to the ion-molecule reactor as described above.

[0163] In addition, the kit or device includes a gas conduit for connecting at least one sampler to the analyte inlet of the ion-molecule reactor, in particular via a multi-port valve. Thus, the gas conduit may include tubes, valves, and / or connectors.

[0164] According to a highly preferred embodiment, the sampler is configured as a sampling unit, in particular an automated sampling unit, which is capable of sequentially collecting analytes from individual samples from a plurality of samples, in particular solid samples (e.g., corks).

[0165] Furthermore, with regard to the sampling unit, it should be noted that it can be used independently of the other components, kits, devices, or equipment of the ion-molecule reactor described herein. For example, the sampling unit can be used in combination with chromatography or extraction if desired.

[0166] In particular, the sampling unit includes a sample holder having a number of chambers, each chamber being configured to receive a single sample. In particular, the sample holder includes 5 - 500 chambers, especially 10 - 150 chambers, preferably 25 - 100 chambers, or approximately 76 chambers.

[0167] In particular, the sampling unit includes a heating unit for heating the sample holder. Preferably, the heating unit includes a controller, a heating element, and / or a temperature sensor for setting a predetermined constant temperature. For example, the heating unit is configured to heat the sample holder to a constant temperature of 30–300 °C, especially 50 - 200 °C, particularly 100 - 150 °C, or approximately 130 °C.

[0168] Preferably, each chamber of the sampling unit includes an inlet and an outlet such that a gaseous fluid stream can pass through each chamber. In particular, all inlets are arranged in a common inlet plane, while all outlets are arranged in a common outlet plane. The inlet plane and the outlet plane are in particular two different planes that are parallel to each other.

[0169] More preferably, the sample holder includes an inlet closing member configured to close and open at least a portion of the inlets of the chambers, and an outlet closing member configured to close and open at least a portion of the outlets of the chambers. Most preferably, the inlet closing member and / or the outlet closing member are configured to dynamically and / or intermittently open and close the chambers, especially such that the chambers or the samples contained within the chambers can remain under substantially non-airtight sealing conditions throughout the period the sample is present within the chamber.

[0170] In particular, the inlet closing member and / or the outlet closing member are movable relative to the sample holder and vice versa, especially such that at least a portion of the inlets of the chambers and / or at least a portion of the outlets of the chambers can be opened and / or closed simultaneously during relative movement between the sample holder and the inlet closing member and / or the outlet closing member.

[0171] In particular, in operation, the sampling unit is configured to continuously move or rotate the sample holder relative to the inlet closure member and / or the outlet closure member, preferably at a substantially constant speed.

[0172] Preferably, the inlet closure member and / or the outlet closure member include a plurality of through openings arranged such that they can be located above at least a portion of the inlet opening and / or the outlet opening of the chamber. Preferably, in order to close the chamber, the through openings in the inlet closure member and / or the outlet closure member can be located above the portion of the sample holder close to the inlet opening and / or the outlet opening of the chamber. In this way, the inlet and / or the outlet of the chamber can be closed by the inlet closure member and / or the outlet closure member.

[0173] In particular, the inlet closure member and / or the outlet closure member only cover a first portion of the sample holder, while a second portion of the sample holder is not covered by the inlet closure member and / or the outlet closure. With this arrangement, the chamber in the second portion of the sample holder is freely accessible, for example for loading or unloading the chamber.

[0174] In particular, the inlet closure member is included in the housing, which allows the delivery of a gaseous fluid to the inlet closure member, in particular to the region of the inlet closure member facing away from the sample holder. Similarly, the outlet closure member is included in the housing, which allows the discharge of the gaseous fluid from the outlet closure member, in particular from the region of the inlet closure member facing away from the sample holder. With this arrangement, the gaseous fluid can pass through the through openings of the inlet closure member via the chamber to the through openings of the outlet closure member and then be discharged from the sampling unit.

[0175] Furthermore, it is preferred to provide channels between adjacent chambers, whereby the channels are configured to create a curtain of gaseous fluid between the adjacent chambers to at least partially separate the inlets and / or outlets of the adjacent chambers. In particular, the channels are configured such that their longitudinal axes extend substantially perpendicular to the longitudinal axis of the chamber. Preferably, the channels are in the form of grooves in a common inlet plane and / or a common outlet plane. Thus, the longitudinal openings of the grooves can be correspondingly covered by the inlet closure member or the outlet closure member.

[0176] In particular, the sampling unit includes at least one removal station for separately recovering the analyte evaporated from the sample in a specific chamber and removing the analyte from the sampler unit, for example via a sampler outlet. In particular, the sample holder is movable relative to the removal station and vice versa, such that the individual chambers can be moved sequentially to the removal station, or such that the removal station can be moved sequentially to the individual chambers. A preferably considered configuration is that the sample holder is movable relative to a fixed removal station.

[0177] Preferably, the removal station includes a gas inlet for introducing a carrier gas into a specific chamber of the sample holder.

[0178] According to a very preferred embodiment, the sample holder includes a hollow cylinder, in particular a hollow annular cylinder, whereby the chamber is present in the wall of the hollow cylinder. In particular, the chamber is designed as a hole whose longitudinal axis preferably extends in a direction parallel to the longitudinal axis of the hollow cylinder, preferably from one end face of the hollow cylinder to the opposite end face. However, a sample holder with a different form can also be provided, for example with a straight body. Preferably, the hole is a cylindrical hole.

[0179] Preferably, the sample holder, in particular in the form of a hollow cylinder, is movably and / or rotatably mounted between an inlet closing member and an outlet closing member, which preferably have through openings arranged at the same spacing as the chamber of the sample holder. Thereby, the inlet closing member and the outlet closing member are preferably mounted in fixed positions in the sampling unit. For example, by rotating the sample holder, the inlet and outlet of the chamber can be opened and closed.

[0180] Even more preferably, the sampling unit is configured such that by moving the sample holder, the through opening of the inlet closing member can be brought into (i) a first position in which the through opening of the inlet closing member is in fluid communication with the inlet of the chamber; (ii) a second position in which the through opening of the inlet closing member is in fluid communication with a channel or groove in a common inlet plane between the chambers; and (iii) a third position in which the through opening of the inlet closing member is located near the inlet opening and the channel. Similarly, the sampling unit is preferably configured such that by moving the sample holder, the through opening of the outlet closing member can be brought into (i) a first position in which the through opening of the outlet closing member is in fluid communication with the outlet of the chamber; (ii) a second position in which the through opening of the outlet closing member is in fluid communication with a channel or groove in a common outlet plane between the chambers; and (iii) a third position in which the through opening of the outlet closing member is located near the outlet opening and the channel.

[0181] Even more preferably, the sampling unit is configured such that an air flow can be provided through the through opening of the inlet closing member. If the through openings of the inlet closing member and the outlet closing member are respectively above at least a part of the inlet opening or the outlet opening of the chamber, these chambers can be flushed with gas. With this arrangement, for example, the sample contained in a specific chamber can be heated in a constant air flow for a certain residence time to accumulate the analyte at the sample surface under uniform temperature conditions and then finally remove the analyte from the chamber in the removal station.

[0182] When the sample holder is moved or rotated, the airflow through the through-opening will be directed to the portion of the chamber adjacent to the sample holder, or to the channels or grooves at the inlet side, which helps to remove the analyte from the through-opening of the inlet closure member. If the through-opening of the outlet closure member is in fluid communication with the channels or grooves at the outlet side, the through-opening of the outlet closure member can be cleaned. In summary, this helps to reduce or eliminate residual contamination between individual chambers or samples. Additionally, this position can be used to obtain reference measurements or zero measurements.

[0183] For example, in operation, the chamber is held under non-gas-tight sealing conditions (e.g., allowing a gaseous fluid to flow through the chamber) for a given time, whereby the inlet closure member and / or the outlet closure member is in the open position. Also, at this time, the analyte present in the removal station can be recovered from a specific chamber. Thereafter, the sample holder can be further moved relative to the inlet closure member and / or the outlet closure member such that the next chamber can be moved to the removal station and vice versa. Thus, during this chamber switching period, the chamber can be closed by the inlet closure member and / or the outlet closure member. Generally, the chamber switching period is shorter, especially much shorter, than the period during which the chamber is in the open position. Therefore, although closing the chamber or the flow of the gaseous fluid through the chamber will stop for a short period of time during the chamber switching period, the sample in the chamber of the sample holder remains substantially under non-gas-tight sealing conditions throughout the entire time the sample is present in the sample holder. This process of dynamically and / or intermittently opening and closing the chamber is in sharp contrast to a system in which the sample is held under gas-tight sealing conditions, for example, during the heating process, and is only opened to recover the analyte accumulated during the heating period.

[0184] According to a preferred embodiment, the sample holder is made of a material different from the inlet closure member and the outlet closure member. Preferably, the sample holder is made substantially of metal, especially steel, especially stainless steel, and most preferably aluminum. This has proven to be an ideal material for maintaining the sample holder at a given and constant temperature. Optionally, the surface of the sample holder can be partially or fully coated with a different material, especially a silicon material (e.g., ), especially plastic materials, preferably polymeric materials, most preferably fluoropolymeric materials such as polytetrafluoroethylene (PTFE). Such coatings are chemically very stable to many substances. The inlet closing member and / or the outlet closing member are preferably made of plastic materials, especially polymeric materials, most preferably fluoropolymeric materials such as polytetrafluoroethylene (PTFE). PTFE can withstand quite high temperatures and is chemically very stable to many substances. The choice of materials helps to achieve high airtightness / good sealing between the sample holder, the inlet closing member and the outlet closure respectively. However, due to the low friction, these elements can still be moved precisely relative to each other. The choice of materials also helps to minimize the memory effect by reducing the adsorption of gas to the walls.

[0185] According to another preferred embodiment, the sampling unit further includes a preheating station. In the preheating station, the sample is preheated to a certain temperature before being introduced into the chamber of the sample holder. This helps to achieve a more uniform temperature distribution in solid samples, especially corks. Overall, this helps to significantly increase the yield of analytes, especially when sampling corks.

[0186] In particular, the preheating station includes a controller, a heating element and / or a temperature sensor for setting a predetermined constant temperature, especially independent of the temperature of the sample holder. For example, the preheating station is configured to heat the sample to a constant temperature of 30–300 °C, especially 50-200 °C, particularly 100-150 °C or about 130 °C. As the heating element, preferably a hot air generating device and / or a heating rod can be used.

[0187] In particular, the preheating station is constructed such that in operation a gaseous fluid flows around the sample. This helps to reduce cross-contamination of the samples.

[0188] For example, in the preheating station, the sample can be held in a separate receptacle, preferably a receptacle open at opposite ends, such that the gaseous fluid can flow through the receptacle. In particular, the receptacle is in the form of a hollow cylinder, especially a cylindrical pipe fitting. This type of receptacle is particularly suitable for corks.

[0189] Preferably, the sampling unit and / or the preheating station further include a loading unit for placing the individual samples in the chamber of the sample holder. In particular, the loading unit can include a conveyor belt, and / or a robotic arm, and / or a two-axis or three-axis manipulator, and / or an alignable feed channel, and / or an alignable guide for transporting the individual samples to the sample holder. In particular, the loading unit is synchronized with the movement of the sample holder, preferably such that the individual samples can be successively loaded into the chamber of the sample holder.

[0190] Preferably, the loading unit is integrated in the preheating station, in particular such that the loading unit can be maintained at the same temperature as the sample. This helps to better maintain the sample at a constant temperature during the entire sampling process.

[0191] According to a very preferred embodiment, the loading unit comprises a movable chain of interconnected receivers, in particular interconnected cylindrical pipe fittings. For example, the movable chain comprises a series of cylindrical pipe fittings, which series of cylindrical pipe fittings are held together by links pivotable about the cylindrical pipe fittings. Preferably, the movable chain comprises two types of alternating links. For example, the first type is an inner link having one or two inner plates around the cylindrical pipe fitting in the central region. These inner links may be alternated with the second type of outer links, which outer links comprise two outer plates around the cylindrical pipe fitting in the end region of the cylindrical pipe fitting.

[0192] Preferably, in order to drive the movable chain, the preheating station comprises a driven gear and optionally one or more additional gears for guiding the movable chain and / or changing the direction of the movable chain.

[0193] In particular, the loading unit is configured such that the movable chain can be at least partially guided above at least one chamber of the sample holder, preferably such that the sample in the receiver can be introduced into the chamber in a vertical movement, for example driven by gravity.

[0194] In summary, the sampling unit as described above is very beneficial because it greatly helps to increase the yield of the analyte evaporated from the sample. This is particularly beneficial for the analysis of haloanisoles in corks as described herein.

[0195] In another preferred embodiment, the kit components are combined into an apparatus for analyzing a sample (in particular a cork), whereby preferably the sampler is connected to the analyte inlet of the ion molecule reactor.

[0196] Another aspect of the present invention relates to a method for generating analyte ions using an ion molecule reactor, in particular an ion molecule reactor as described above, the method comprising the steps of:

[0197] a) introducing the analyte into the reaction volume of the chamber through the analyte inlet;

[0198] b) providing reagent ions and introducing the reagent ions into the reaction volume;

[0199] c) causing the reagent ions to interact with the analyte to form analyte ions;

[0200] d) optionally guiding the reagent ions and / or the analyte ions along a predetermined path through the reaction volume using an ion guide, preferably using an alternating electric field, magnetic field and / or electromagnetic field;

[0201] Preferably, the analyte is introduced into the reaction volume along an inlet path into the reaction volume, where the inlet path extends substantially along at least a first part of a predetermined transport path in the reaction volume.

[0202] Accordingly, steps c) and d) can be carried out at least partially simultaneously. In other words, when guiding the reagent ions along at least a part of the transport path, the reagent ions can interact with the analyte to form analyte ions.

[0203] According to a preferred method, the analyte is introduced into the reaction chamber in the form of a mixture with at least one other chemical substance, in particular with a plurality of other chemical substances, in particular with at least 5, 10, 100, 1000, 10000 or 100000 different other chemical substances. The other chemical substances can be components of a complex mixture to be analyzed and / or substances of a carrier gas used to introduce the analyte into the reaction chamber. Generally, the other chemical substances are volatile organic compounds, inert gas atoms and / or air components.

[0204] In particular, the mixture is a homogeneous gaseous mixture. However, a non-homogeneous gaseous mixture, such as an aerosol, is also possible.

[0205] In particular, the analyte comprises or consists of a volatile organic compound having a boiling point of less than or equal to 300 °C measured at a standard atmospheric pressure of 101.3 kPa, optionally having a boiling point above 300 °C.

[0206] In particular, the mixture comprises or consists of vapors of substances evaporated from cork (especially cork stoppers). In particular, the analyte comprises or consists of haloanisoles and / or halophenols. In particular, the analyte comprises at least one compound selected from the group consisting of 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), 2,3,4,5,6-pentachloroanisole (PCA) and 2,4,6-tribromoanisole (TBA) or consists of the same. In particular, the analyte comprises 2,4,6-trichloroanisole (TCA) or consists of the same.

[0207] In particular, the mixture further comprises a carrier gas, such as air, N 2 or an inert gas, such as Kr and / or Ar.

[0208] In particular, the concentration of the analyte (especially haloanisole) in the mixture is 100 ppt or lower, especially 1 ppt or lower, particularly 0.1 ppt or lower, for example 0.01 ppt or lower, especially 0.001 ppt or lower.

[0209] Particularly preferably, in the method of the present invention, the pressure in the ion-molecule reactor is below 100 mbar, preferably below 10 mbar, particularly below 1 mbar. In such a pressure range, the efficiency of the ionization reaction and the yield of analyte ions are surprisingly high. This particularly allows for the measurement of ultra-low concentrations of analytes, such as analytes in the range of a few ppq.

[0210] Although less preferred, for special purposes, the method of the present invention can also be carried out at a pressure of 10 kPa or higher, particularly 100 kPa or higher.

[0211] Particularly, analyte ions are generated from the analyte and reagent ions by chemical ionization.

[0212] Particularly, analyte ions are generated from the analyte and reagent ions by proton transfer reaction (PTR). Therefore, hydronium ions are used as reagent ions.

[0213] In combination with the method of the present invention, particularly in combination with analytes in the form of volatile organic compounds, this has proven to be very beneficial. However, other reagent ions can also be used, such as the reagent ions described above in connection with the ion-molecule reactor of the present invention.

[0214] Therefore, particularly, the reagent ions are selected from H 3 O + 、O 2 + 、CH 4 + 、NH 4 + 、isobutane ions, inert gas ions and / or NO + . However, in principle, negatively charged reagent ions can also be used.

[0215] For example, with regard to halogenated anisoles, it has proven to be very beneficial to generate analyte ions from the analyte by charge transfer reaction. Therefore, positively charged reagent ions such as O 2 + and / or NO + , particularly NO + are particularly preferred.

[0216] In a specific embodiment, different reagent ions, such as O 2 + and NO + can be used simultaneously or alternately. When used alternately, for example, different ion sources are used intermittently. The different ions can have the same polarity or opposite polarities. In general, using different reagent ions can help to further improve selectivity.

[0217] Thus, analyte ions are preferably generated from the analyte and reagent ions by proton transfer reactions and / or charge transfer reactions.

[0218] Thus, in a preferred embodiment, particularly with respect to haloanisoles, reagent ions are selected to interact with the analyte in a charge transfer chemical ionization reaction. In this case, the reagent ions are specifically selected such that the population of the unprotonated analyte ions (M + ) formed is greater than the population of the protonated analyte ions (MH + ). Thus, preferably, the reagent ions are selected not to interact with the analyte by proton transfer reactions.

[0219] Preferably, the analyte ions generated in the ion-molecule reactor are introduced into a mass analyzer, particularly a time-of-flight mass analyzer, a quadrupole mass analyzer, an ion trap analyzer, a sector field mass analyzer, a Fourier transform ion cyclotron resonance analyzer, and / or an orbitrap.

[0220] In particular, the analyte ions are introduced into the mass analyzer without otherwise affecting the chemical and / or physical properties of the analyte ions. In particular, the analyte ions are introduced into the mass analyzer without any additional separation steps. Preferably, the analyte ions are introduced into the mass analyzer without passing through chromatography, extraction, ion mobility separation, gas chromatography, liquid chromatography, solid-phase microextraction, and / or headspace solid-phase microextraction.

[0221] With the method of the present invention, separation steps are not required. However, high sensitivity can be achieved. However, for specific applications, additional separation steps can be optionally contemplated.

[0222] In particular, in the ion-molecule reactor, reagent ions and / or analyte ions are guided, focused, accelerated, and / or decelerated within the reaction volume and / or along a predetermined transport path with alternating electric, magnetic, and / or electromagnetic fields, particularly in combination with the ion-molecule reactor as described above.

[0223] In particular, a guiding field is generated for guiding and / or focusing ions, particularly analyte ions and / or reagent ions, along the transport path. The guiding field is preferably an electromagnetic field, particularly a radio frequency (RF) field, which generates an effective electric potential that confines the ions to a region along the transport path.

[0224] Preferably, a transport field is generated for accelerating and / or decelerating the ions in the direction along the transport path. Preferably, the transport field is an electric field that extends substantially along the transport path, particularly a DC field.

[0225] In particular, a rotating field is generated, particularly for setting a substantially constant energy of the ions. Preferably, the rotating field results in ion motion that traces a path around the average flight path of the ions.

[0226] More preferably, a transport field and a guiding field are generated simultaneously. Most preferably, a rotational field is also generated in addition to the transport field and the guiding field. This allows the velocity of ions along the transport path to be controlled in a very efficient manner independently of the focusing and / or guiding of the ions.

[0227] To generate these fields, electrodes, voltage generating devices and other components related to the ion molecule reactor as described above can be used. In addition, it is preferred to carry out the method of the invention with an ion guide, such as a multipole assembly, an ion funnel, an ion blanket or a combination thereof as described above.

[0228] In particular, the ion molecule reactor and / or the transport path is at least partially surrounded by a tubular element, especially as described above.

[0229] In another preferred method, a fluid is introduced into the reaction volume through at least one porous and / or gas-permeable part of the tubular element.

[0230] In particular, a sheath gas or a buffer gas is introduced into the reaction volume, for example, to reduce wall effects or memory effects due to the pressure difference between the internal pressure and the external pressure of the tubular element, or to dilute the analyte. However, reagent gas and / or reagent ions can also be introduced into the reaction volume through at least one porous part of the tubular element. In this case, at least one porous part of the tubular element has the function of a reagent ion inlet.

[0231] According to a very advantageous method, neutrals and / or ions that have left a predetermined transport path are removed from the reaction volume and / or the ion molecule reactor through at least one porous and / or gas-permeable part of the tubular element.

[0232] Details of the tubular element and of at least one porous and / or gas-permeable part have been described above in connection with the ion molecule reactor. Preferably, the tubular element is included within an external tubular element as described above.

[0233] In the following, a very preferred method for analyzing a sample (in particular a cork) is described. The method comprises the steps of:

[0234] a) collecting at least one analyte from a sample containing at least one analyte, in particular a halogenated anisole, in particular using a sampler as described above;

[0235] b) generating analyte ions from at least one analyte by the method described above;

[0236] c) analyzing the analyte ions, in particular using a mass analyzer as described above, for example.

[0237] Preferably, in step a), at least one analyte is collected by heating under conditions suitable for or effecting the evaporation of at least one analyte present in the sample.

[0238] In particular, the sample is a solid sample. However, the sample can also be a liquid sample, a gas sample, and / or a heterogeneous sample comprising mixed phases.

[0239] In particular, the sample comprises or consists of cork, in particular, the sample is a cork stopper, and heating is carried out under conditions suitable for or effecting the evaporation of haloanisoles and / or halophenols. In particular, heating is carried out under conditions suitable for or effecting the evaporation of 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), 2,3,4,5,6-pentachloroanisole (PCA), and 2,4,6-tribromoanisole (TBA) that may be present in the cork.

[0240] In particular, heating the sample and / or collecting the analyte is effected under substantially constant pressure conditions. Thus, a sampler with an overpressure vent as described above can be used.

[0241] At least one analyte collected in step a) is preferably mixed with a carrier gas and introduced into the reaction volume as a mixture in step b). Thus, in particular, the carrier gas is selected from N 2 or an inert gas (such as Kr, Ar) and / or selected from purified air. The mixture is in particular guided from the outlet of the sampler through a gas conduit system to the analyte inlet of the ion molecule reactor.

[0242] For mixing, the carrier gas is preferably guided to flow at least along a part of the sample surface, in particular along a part of the cork stopper surface. This allows the evaporated analyte that may adhere to the sample surface to be absorbed by the carrier gas.

[0243] In particular, before mixing, the carrier gas is preferably heated to a temperature suitable for effecting the evaporation of at least one analyte present in the sample. Under such conditions, the risk of recondensation of the analyte due to cooling or damage to the analyte due to excessive heat can be reduced.

[0244] Preferably, once the mixture is introduced into the reaction volume, the carrier gas is continuously supplied and the carrier gas flows at least along a part of the sample surface. Thus, the analyte evaporated from the sample can be continuously absorbed, resulting in a well-defined analyte stream entering the reaction volume. Thus, according to a preferred embodiment, after being collected in step a), the analyte collected in step a) is continuously introduced into the reaction volume in step b).

[0245] Preferably, steps a) and b) occur in real time. Thereby, in particular, immediately after collection in step a), the analyte collected in step a) is introduced into the reaction volume in step b). This allows for the direct analysis of the analyte in real time. However, for specific applications, the analyte can first be collected in step a) for a defined period of time and then introduced into the reaction volume in step b) at a later time.

[0246] In particular, a mixture containing at least one analyte ion is introduced into the reaction volume in step b) without otherwise affecting the chemical and / or physical properties of the mixture. In particular, the analyte ions are introduced into the reaction volume without any additional separation steps. Preferably, the analyte ions are introduced into the reaction volume without any chromatographic analysis, extraction, ion mobility separation, gas chromatography, liquid chromatography, solid-phase microextraction, and / or headspace solid-phase microextraction.

[0247] According to another preferred method, before collecting at least one analyte in step a), the sample is heated, in particular such that a gaseous fluid flows around the sample for a given residence time. In particular, heating includes preheating at a first temperature and main heating at a second temperature. In particular, the second temperature is higher than the first temperature. For example, the first temperature and / or the second temperature is 30–300 °C, especially 50 - 200 °C, particularly 100 - 150 °C or about 130 °C. This allows the analyte to accumulate on the sample surface under uniform temperature conditions.

[0248] Particularly preferably, when using a sampler (e.g., the sampling unit described above) capable of collecting analytes from multiple samples, in order to reduce cross-contamination, a curtain of gaseous fluid is created between adjacent samples.

[0249] Particularly preferably, when using the sampling unit described above, at least during steps a), b), and / or c), the sample holder is continuously moved and / or rotated relative to the inlet closing member and / or the outlet closing member, preferably at a substantially constant speed. Thus, individual samples such as corks can be analyzed in sequence, and reference measurement values can be obtained between two sample measurements.

[0250] Preferably, in order to collect the analyte, a carrier gas flows around the sample, and thereby preferably, during heating, the flow rate of the carrier gas is higher than the flow rate of the gaseous fluid.

[0251] In particular, during heating and / or when collecting the analyte, the sample is maintained at a pressure higher than the ambient pressure. This helps to reduce contamination.

[0252] Using the method of the present invention, no separation step is required. In short, this will significantly accelerate the analysis speed. However, high sensitivity can be achieved. However, for specific applications, additional separation and / or concentration steps can be optionally envisaged.

[0253] Using the above method for analyzing a sample, the sampler and / or sampling unit as described above is preferably used in step a).

[0254] In particular, the sampler includes a heatable container for receiving the sample, the container including an opening for inserting the sample into the container, an inlet for introducing a gaseous fluid into the interior of the container, and an outlet for recovering the gaseous fluid. The container preferably includes a breathable element or closure such that the interior of the container communicates with the exterior of the container and / or the exterior of the sampler.

[0255] According to a preferred embodiment, the sample (in particular a cork) is inserted into the opening for inserting the sample into the container, whereby the sample is surrounded by the opening in the contact area. In particular, the opening of the container is selected such that it has a shape complementary to the shape of one end of the sample so that the opening is closed by the sample when the sample is present in the container.

[0256] According to another preferred embodiment, the sample (in particular a cork) is inserted into the container and / or the opening such that when the sample is present in the container, a free passage is left between the container and / or the opening.

[0257] In particular, the sample is inserted into the container such that when the sample is placed in the container, it does not contact the container and / or the opening.

[0258] Most preferably, the sampler is configured as a sampling unit, in particular an automatic sampling unit, which is capable of sequentially collecting the analytes of individual samples from a plurality of samples (in particular solid samples, such as corks). The sampling unit is configured as described above in particular.

[0259] Another aspect of the present invention is the use of the ion-molecule reactor as described above in mass spectrometry analysis and / or in use with a mass spectrometer. Thus, the mass spectrometer or mass analyzer for mass spectrometry analysis is defined as described above.

[0260] Furthermore, the present invention relates to the use of the ion-molecule reactor, kit, device and / or equipment as described above for analyzing a gaseous mixture containing at least one analyte substance and in particular at least 5, 10, 100, 1000, 10000 or 100000 different other chemical species.

[0261] Another aspect of the present invention relates to the use of the ion-molecule reactor, kit, device and / or equipment as described above for analyzing whether a cork is contaminated with cork taint.

[0262] Furthermore, another aspect of the present invention relates to the use of the ion-molecule reactor, kit, device, and / or equipment as described above for analyzing the presence of halobenzene ethers and / or halophenols, in particular 2,4,6-trichlorobenzene ether (TCA), 2,3,4,6-tetrachlorobenzene ether (TeCA), 2,3,4,5,6-pentachlorobenzene ether (PCA), and 2,4,6-tribromobenzene ether (TBA), and / or their proportions in a sample.

[0263] It should also be noted that the tubular element comprising at least one porous and / or breathable part as described above can be used independently of the other components of the ion-molecule reactor described herein. For example, a tubular element comprising at least one porous and / or breathable part can be used instead of the ion guide according to the present invention. However, the tubular element comprising at least one porous and / or breathable part can also be used for other applications.

[0264] Accordingly, another aspect of the present invention relates to a tubular element comprising at least one porous and / or breathable part, particularly for use as an ion transport tube and / or an ion-molecule reactor. In particular, at least one porous or breathable part is an annular or ring-shaped part of the tubular element. In a particular embodiment, the tubular element is porous and / or breathable along its entire length.

[0265] According to another preferred embodiment, the tubular element comprising at least one porous and / or breathable part is included within the outer tubular element as described above. Thus, in particular, the outer tubular element is airtight or non-porous. For example, the outer tubular element is made of stainless steel.

[0266] In particular, the inner diameter of the outer tubular element is greater than the outer diameter of the tubular element. Thus, in this case, there is a free volume between the tubular element and the outer tubular element. This volume can be used, for example, to provide a fluid, such as a gas, which is introduced into the reaction volume through the porous part of the tubular element. The pressure within the free volume can also be reduced to a value lower than the pressure within the reaction volume in order to remove, for example due to the pressure difference, neutral analytes and / or other substances from the reaction volume.

[0267] Preferably, the outer tubular element includes an opening for introducing a fluid and / or for evacuating the free volume between the two tubular elements.

[0268] In particular, the tubular element comprising at least one porous and / or breathable part includes at least one electrode as described above. Other preferred features of the tubular element have been described above.

[0269] In particular, the tubular element comprising at least one porous and / or breathable part is part of an ion-molecule reactor and / or a mass spectrometer.

[0270] If a tubular element comprising at least one porous and / or breathable part is used as an ion-molecule reactor, it preferably comprises a reagent ion source as described above.

[0271] In particular, a tubular element comprising at least one porous and / or breathable part can be used instead of the ion guide in the ion-molecule reactor as described above.

[0272] Accordingly, another aspect of the present invention is an ion-molecule reactor for generating analyte ions from an analyte, particularly for use with a mass spectrometer and / or in mass spectrometry analysis, the ion-molecule reactor comprising:

[0273] a) a reaction volume in which reagent ions can interact with the analyte to form analyte ions, particularly by chemical ionization;

[0274] b) at least one tubular element comprising at least one porous and / or breathable part surrounding the reaction volume, at least partially for guiding reagent ions and / or analyte ions along a predetermined transport path through the reaction volume;

[0275] c) at least one analyte inlet allowing the analyte to be introduced into the reaction volume along an inlet path, whereby the direction of the inlet path extends substantially along the direction of at least a first part of the predetermined transport path in the reaction volume;

[0276] d) at least one reagent ion source and / or at least one reagent ion inlet allowing reagent ions to be provided into the reaction volume.

[0277] Thus, preferably, at least one reagent ion source and / or at least one reagent ion inlet is located radially outward with respect to the first part of the predetermined path, the analyte inlet and / or the direction of the inlet path, and is configured such that reagent ions can be introduced into the reaction volume along at least two different directions and / or from at least two different positions.

[0278] With such a device, a fluid can be introduced from the outside to the inside of the tubular element through the porous and / or breathable part. The fluid can be, for example, a reagent gas, reagent ions, sheath gas and / or buffer gas. In particular, if the fluid is introduced along the radial direction, the incoming fluid effectively prevents atoms and / or molecules (such as analytes and / or analyte ions) from reaching the inner wall of the tubular element. However, compared with the prior art systems, a high-pressure laminar flow of sheath gas is not required.

[0279] Combinations of other advantageous embodiments and features result from the following detailed description and the overall claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0280] The accompanying drawings used to explain the embodiments show:

[0281] Figure 1 is a cross-section of a first ion-molecule reactor having an annular reagent ion inlet surrounding an analyte inlet and an ion guide composed of a multipole electrode assembly;

[0282] Figure 2 is a cross-section of a second ion-molecule reactor having two separate reagent ion inlets diametrically opposedly mounted in a cylindrical outer peripheral surface of a housing of a chamber and an ion guide composed of a multipole electrode assembly;

[0283] Figure 3 is a cross-section of a third ion-molecule reactor having a housing and an external tubular element, the housing including a gas-permeable portion, the external tubular element surrounding the housing to remove fluid from and / or introduce fluid into the reaction volume accordingly. Additionally, the third ion-molecule reactor has a multipole electrode assembly within an annular free volume between the tubular element and the housing, the multipole electrode assembly capable of generating a rotating multipole field during operation. Furthermore, an ion funnel is disposed outside the housing where analyte ions exit the housing of the ion-molecule reactor;

[0284] Figure 4 is a cross-section of a fourth ion-molecule reactor having an ion guide composed of a multipole electrode assembly and further including an integrated ion source that allows introduction of reagent ions through the gas-permeable portion of the housing;

[0285] Figure 5 is a mass spectrometry device including Figure 2 the second ion-molecule reactor as well as a differential pumping stage and a mass analyzer;

[0286] Figure 6 is a cross-section of a fifth ion-molecule reactor including a gas-permeable portion along the entire length of the reaction volume;

[0287] Figure 7 is a cross-section of a sixth ion-molecule reactor including an ion guide composed of a multipole electrode assembly and incorporating an ion funnel;

[0288] Figure 8 is a cross-section of a seventh ion-molecule reactor including an ion guide composed of an ion blanket;

[0289] Figure 9is a cross-section of an eighth ion-molecule reactor, the eighth ion-molecule reactor comprising a reagent ion inlet with an additional guiding element and an ion funnel serving as an ion guide, the reagent ion inlet and the ion funnel being connected to separate voltage generators;

[0290] Figure 10 is along Figure 3 a top view along the longitudinal axis of the ion funnel of the ion-molecule reactor shown;

[0291] Figure 11 is along Figure 8 a top view along the longitudinal axis of the ion blanket used in the ion-molecule reactor shown;

[0292] Figure 12 is a cross-section along the longitudinal axis of a headspace sampler for a cork;

[0293] Figure 13 is Figure 12 the headspace sampler connected to Figure 5 the device shown;

[0294] Figure 14 is a schematic diagram of an automatic sampling unit for analyzing a cork. With this unit, the cork can be moved step by step on a conveyor belt, whereby the sampler is placed sequentially above the cork to be analyzed by a linear manipulator;

[0295] Figure 15 is four Figure 12 the sampler shown connected to a multi-port valve for switching between the individual samplers;

[0296] Figure 16a is a top view of a sample holder comprising a number of chambers for accommodating a plurality of samples;

[0297] Figure 16b is along Figure 16a a cross-section along line A-A of the sample holder;

[0298] Figure 17a is a device comprising a removal station for removing an analyte from a specific chamber and Figure 16a the sample holder, wherein a part of the chambers is covered by an inlet closing member and an outlet closing member (not visible in Figure 17a );

[0299] Figure 17b is Figure 17a the device along Figure 17a a detail of a cross-sectional view along the dashed line in, wherein the through openings in the inlet closing member and the outlet closing member are centered above the chambers such that the ends of the chambers are open;

[0300] Figure 17c is Figure 17b an apparatus in which the sample holder has been rotated to a position where the chamber is closed;

[0301] Figure 17d is Figure 17b an apparatus in which the sample holder has been rotated to a position where the through-opening of the inlet closing member and the through-opening of the outlet closing member are in fluid communication with the recess in the sample holder;

[0302] Figure 18 is a schematic view of an apparatus for measuring an analyte from a solid sample such as a cork, the apparatus comprising Figure 17a the apparatus, a preheating station, a loading unit and an ion-molecule reactor;

[0303] Figure 19 is a perspective view of the preheating station in which the sample is held in an open receiver, the receiver being part of a movable chain;

[0304] Figure 20 is Figure 19 a part of the movable chain used in the preheating station.

[0305] In the drawings, like parts are given like reference numerals. Detailed Description

[0306] Figure 1 shows a cross-section of a first ion-molecule reactor 100. The ion-molecule reactor 100 includes a hollow cylindrical housing 110 having a longitudinal axis 111 and a reaction volume 140 inside the housing 110. Thus, the housing 110 forms a tubular element surrounding the reaction volume. The housing is made of, for example, lead-doped silicate glass and has a resistive layer on the inner side. The length of the housing in the longitudinal direction is, for example, 100 mm, the inner diameter is 10 mm, and the outer diameter is 13 mm. The resistance between the right axial end 113 and the left axial end 114 of the housing 110 is, for example, 1 GΩ.

[0307] On Figure 1 the right side of Figure 1 , the housing 110 has a circular opening 112 concentric with the longitudinal axis 111 at the right axial end 113. The circular opening is an exit orifice, for example with a pore diameter of 1 mm. On Figure 1 the left axial end 114 of Figure 1 , a hollow cylindrical analyte inlet 120 extends along the longitudinal axis 111 of the ion-molecule reactor 100. An analyte 121 (e.g., a volatile organic compound) can be introduced into the reaction volume 140 through the analyte inlet 120 along an inlet path 122. The inlet path 122 of the analyte extends along a predetermined transport path 141 in the reaction volume 140, whereby the transport path 141 extends along the longitudinal axis 111 of the housing 110.

[0308] Also on the Figure 1 left side of, the annular or circular reagent ion inlet 130 is arranged concentrically around the analyte inlet 120. Thus, the reagent ion inlet 130 is positioned radially outward with respect to the predetermined transport path 141 and the inlet path 122. Due to the annular or circular form, the reagent ions 131 can be introduced into the reaction volume 140 from substantially all positions on the annular opening. The reagent ions are generated in a reagent ion source (e.g., a conventional plasma discharge reagent ion source) ( Figure 1 not shown in the figure).

[0309] In operation, the analyte 121 undergoes chemical ionization upon collision with the reagent ions 131. Thereby, charged analyte ions 123 are formed.

[0310] To guide the analyte ions and the reagent ions along the transport path 141 through the reaction volume 140, the first ion-molecule reactor 100 includes an ion guide formed by a plurality of electrodes. Specifically, the housing 110 is surrounded by a set of four cylindrical rod-shaped electrodes 150, 151 (only two electrodes can be seen in Figure 1 the figure). All the rod-shaped electrodes 150, 151 are regularly arranged around the housing 110 at equal angular distances and extend in a direction parallel to the longitudinal axis 111 of the housing 110. In operation, the four rod-shaped electrodes 150, 151 are connected to an RF generating device (not shown), and two opposite rod-shaped electrodes 150, 151 are each connected in parallel. A pure RF voltage, for example with a frequency of 1 - 10 MHz, is applied between adjacent electrodes. Thereby, a multipole guiding field is generated, which allows guiding and focusing the analyte ions 123 and the reagent ions 131 along the transport path 141.

[0311] In addition, a voltage generating device (not shown) can be connected between the right axial end 113 and the left axial end 114 of the housing, and this voltage generating device allows applying a voltage and generating a transport field (DC field) that extends parallel to the longitudinal axis 111 of the housing 110. Thus, the housing itself serves as another electrode. The transport field allows the ions to be accelerated and / or decelerated towards the opening 112 at the right axial end.

[0312] The four cylindrical rod-shaped electrodes 150, 151 and the housing 110 together constitute an effective ion guide that allows selectively guiding the ions in the reaction volume 140 without affecting the neutrals.

[0313] Figure 2A cross-section of a second ion-molecule reactor 200 is shown. Except for the reagent ion inlet, the ion-molecule reactor 200 is substantially the same as the first ion-molecule reactor 100. Accordingly, all the elements and components 210, 211, 212, 213, 214, 220, 221, 222, 223, 231, 240, 241, 250, and 251 of the second reactor 200 correspond to the elements and components 110, 111, 112, 113, 114, 120, 121, 122, 123, 131, 140, 141, 150, and 151 of the first reactor 100. For example, the analyte inlet 220 of the second ion-molecule reactor 200 is substantially the same as the analyte inlet 120 of the first ion-molecule reactor 100, and so on.

[0314] However, the second ion-molecule reactor 200 does not include an annular reagent ion inlet arranged concentrically around the analyte inlet as in the first ion-molecule reactor 100. Instead, the second ion-molecule reactor 200 includes two separate analyte inlets 230a, 230b, which are diametrically opposed and mounted in the cylindrical outer surface of the housing 210 at a location near the left axial end 214. Both analyte inlets 230a, 230b are hollow cylindrical tubes that extend in a direction orthogonal to the longitudinal axis 211 of the ion-molecule reactor 200. Accordingly, reagent ions 231 can be introduced into the reaction volume 240 from substantially two different locations and in opposite directions, each direction being substantially perpendicular to the longitudinal axis 211. Further, in this case, the reagent ions 231 are generated in a reagent ion source (e.g., a conventional plasma discharge reagent ion source) ( Figure 2 not shown).

[0315] Without being bound by theory, it is believed that due to the introduction of the reagent ions from two opposite directions, the reagent ions are decelerated in front of the analyte inlet 220 due to electrostatic repulsion and are captured by the ion guiding elements, namely, four cylindrical rod-shaped electrodes 250, 251 ( Figure 2 only two of the four electrodes are shown) and the housing 210.

[0316] Figure 3Shows a cross-section of a third ion-molecule reactor 300 that is partially similar to the second ion-molecule reactor 200. Specifically, all elements and components 310, 311, 312, 313, 314, 320, 321, 322, 323, 330a, 330b, 331, 340, 341, 350, and 351 of the third reactor 300 correspond to the elements and components 210, 211, 212, 213, 214, 220, 221, 222, 223, 230a, 230b, 231, 240, 241, 250, and 251 of the second reactor 200. For example, the analyte inlet 320 of the third ion-molecule reactor 300 is substantially the same as the analyte inlet 220 of the second ion-molecule reactor 200, and so on.

[0317] However, in addition to the second ion-molecule reactor 200, the third ion-molecule reactor 300 further includes a hollow cylindrical outer tubular element 370, which is made of, for example, stainless steel and concentrically surrounds the housing 310 over most of its length. The inner diameter of the outer tubular element 370 is greater than the outer diameter of the housing 310, such that four rod-shaped electrodes 350, 351 are located within the annular free volume 372 between the housing 310 and the outer tubular element 370. At the outer surface of the outer tubular element 370, an opening 371 is installed for introducing fluid and / or evacuating the free volume 372 between the two tubular elements.

[0318] In addition, the housing 310 includes an annular and gas-permeable portion 360, made of, for example, frit, in the portion surrounded by the outer tubular element 370. Except for the opening 371 and the gas-permeable portion 360, the outer tubular element is mounted on the housing 310 in an airtight manner. Thus, the tubular housing 310 includes a non-porous or airtight first portion and a porous or gas-permeable second portion.

[0319] In operation, when evacuating the free volume 372 between the two tubular elements 310, 370, neutrals (such as non-ionized analyte 321) or ions that have left the transport path 341, the path, can be removed from the reaction volume 340 and the ion-molecule reactor 300 via the opening 371. Thus, a conventional vacuum pump ( Figure 3 not shown in

[0320] In addition, the ion-molecule reactor 300 includes an ion funnel 380, which is arranged outside the housing 310 behind the opening 312 at the right axial end 313. The ion funnel 380 consists of a stack of four metal ring electrodes 381 with a gradually decreasing inner diameter. This allows for the specific extraction of analyte ions from the reaction volume 340 in a defined direction and with high yield. Figure 10 Shows a top view of the ion funnel 380.

[0321] In addition, if a suitable rotating multipole field is generated by using four cylindrical rod electrodes 350, 351 during operation, the analyte ions 323 can be transported toward the opening 312 while spiraling along an average flight path around a helical trajectory ( Figure 3 the virtual helix in).

[0322] Figure 4 A cross-section of a fourth ion-molecule reactor 400 is shown, which is partially similar to the third ion-molecule reactor 300. Specifically, all elements and components 410, 411, 412, 413, 414, 420, 421, 422, 423, 431, 440, 441, 450, 451, 470, 471, and 472 of the fourth reactor 400 correspond to the elements and components 310, 311, 312, 313, 314, 320, 321, 322, 323, 331, 340, 341, 350, 351, 370, 371, and 372 of the third reactor 300. For example, the analyte inlet 420 of the fourth ion-molecule reactor 400 is substantially the same as the analyte inlet 320 of the third ion-molecule reactor 300, and so on.

[0323] However, with the fourth reactor 400, there is no separate analyte inlet mounted diametrically opposite in the cylindrical outer surface of the housing. Instead, the housing 410 includes an annular and breathable portion 460 in the portion surrounded by the outer tubular element 470, and the annular and breathable portion 460 is arranged near the left axial end 414. Radially outward, an annular x-ray source 490 is mounted on the outer surface of the outer tubular element 470.

[0324] During operation, a neutral reagent 431a can be introduced into the annular free volume 472 between the housing 410 and the outer tubular element 470. Therefore, the pressure in the annular free volume 472 is selected to be higher than the pressure in the reaction volume 440, so as to force the reagent to pass through the breathable portion 460 and enter the reaction volume 440. In the region of the x-ray source, the neutral reagent is ionized by the x-ray, such that the breathable portion 460 serves as an annular reagent ion inlet, providing reagent ions from all radial directions perpendicular to the longitudinal axis 411.

[0325] Figure 5 A schematic diagram of a mass spectrometer 500 is shown, and the mass spectrometer 500 includes a second ion-molecule reactor 200 as Figure 2 described. Thus, the analyte ions exiting from the circular opening 212 of the ion-molecule reactor are sent to an optional differential pumping interface 501 to further reduce the pressure, and then enter a mass analyzer 502, such as a time-of-flight mass analyzer.

[0326] Figure 6Shows a cross-section of a fifth ion-molecule reactor 600. The ion-molecule reactor 600 includes a hollow cylindrical housing 610 having a longitudinal axis 611 and a reaction volume 640 within the housing 610. Thus, the housing 610 forms a tubular element surrounding the reaction volume 640. At the circular left and right end sides 613, 614, the housing is made of, for example, stainless steel, while the entire curved surface area of the housing 610 is made of an annular and gas-permeable part 660 (such as a frit).

[0327] In addition, a hollow cylindrical outer tubular element 670 (which is made of, for example, stainless steel) concentrically surrounds the housing 610 over the entire length of the housing 610. The inner diameter of the outer tubular element 670 is greater than the outer diameter of the housing 610 such that an annular free volume 672 is formed between the housing 610 and the outer tubular element 670. An opening 671 for introducing a fluid, such as a neutral reagent gas 631a, is installed at the outer surface of the outer tubular element 670. Radially outward, an annular x-ray source 690 is mounted on the outer surface of the outer tubular element 670.

[0328] On Figure 6 the right side of, the housing 610 has a circular opening 612 concentric with the longitudinal axis 611 at the right axial end 613. On Figure 6 the left axial end 614 of, a hollow cylindrical analyte inlet 620 extends along the longitudinal axis 611 of the ion-molecule reactor 600. An analyte 621 (such as a volatile organic compound) can be introduced into the reaction volume 640 through the analyte inlet 620 along an inlet path 622. The inlet path 622 of the analyte extends along a predetermined transport path 641 within the reaction volume 640, where the transport path 641 extends along the longitudinal axis 611 of the housing 110.

[0329] In operation, the neutral reagent gas 631a is ionized by the x-ray source 690 to form reagent ions 631, and the reagent ions 631 are radially introduced into the reaction volume 640 through the gas-permeable part 660. Thus, once colliding with the reagent ions 631, the analyte 621 in the reaction volume 640 will undergo chemical ionization. Charged analyte ions 123 are thereby formed. Due to the radial flow of the reagent ions 631, the flow of the analyte 621 and the analyte ions 641 towards the wall or the gas-permeable part 660 is correspondingly reduced or inhibited.

[0330] Figure 7 Shows a cross-section of a sixth ion-molecule reactor 700, which is similar to Figure 1The first ion-molecule reactor 100 shown. Specifically, all elements and components 710, 711, 712, 713, 714, 720, 721, 722, 723, 730, 731, 740, 741, 750, and 751 of the sixth chamber 700 correspond to the elements and components 110, 111, 112, 113, 114, 120, 121, 122, 123, 130, 131, 140, 141, 150, and 151 of the first reactor 100. For example, the analyte inlet 720 of the sixth ion-molecule reactor 700 is the same as the analyte inlet 120 of the first ion-molecule reactor 100, and so on.

[0331] In addition, the sixth reactor includes an ion funnel 780 that is located within the housing 710 in front of the right axial end 713. The ion funnel 780 includes a stack of four metal ring electrodes 781 and is Figure 3 and Figure 10 substantially the same as the ion funnel 380 shown. The electrodes 781 of the ion funnel 780 are coaxial with respect to the transmission path 741 or the longitudinal axis 711 accordingly. In operation, the four ring electrodes 781 are connected to an RF generating device (not shown), whereby an alternating RF potential of typically 0.1 - 10 MHz frequency is applied to adjacent electrodes such that charged analyte ions 723 are radially confined as they pass through the ion funnel 780.

[0332] Figure 8 A cross-section of a seventh ion-molecule reactor 800 is shown, which is partially similar to Figure 2 the second ion-molecule reactor 200 shown. Specifically, all elements and components 810, 811, 812, 813, 814, 820, 821, 822, 823, 830a, 830b, 831, 840, and 841 of the seventh reactor 800 correspond to the elements and components 210, 211, 212, 213, 214, 220, 221, 222, 223, 230a, 230b, 231, 240, and 241 of the second reactor 200. For example, the analyte inlet 820 of the seventh ion-molecule reactor 800 is the same as the analyte inlet 220 of the second ion-molecule reactor 200, and so on.

[0333] However, the ion-molecule reactor 800 does not include any rod-shaped electrodes. Instead, the seventh reactor 800 includes an ion blanket 880 that is located within the reaction volume 840, near the analyte inlet 820 and the reagent ion inlets 830a, 830b. The ion blanket 880 consists of a substantially planar arrangement of five metal toroidal electrodes 881 that are concentrically mounted on an insulating support having a central orifice. The electrodes 881 of the ion blanket 880 and the central orifice are coaxial with respect to the transport path 841 or the longitudinal axis 811, respectively. Figure 11 A top view of the ion blanket 800 along the longitudinal axis 811 is shown.

[0334] In operation, the five toroidal electrodes 881 are connected to an RF generating device (not shown), and a voltage is applied to the electrodes 881 to create an alternating electric field typically having a frequency of 0.1 - 10 MHz, which causes the reagent ions and / or analyte ions to converge through the central orifice. Thereby, a guiding field is created that allows the analyte ions 823 and reagent ions 831 to be guided and focused along the transport path 841. A similar device and its operation are described, for example, in US2013 / 0120897 A1 (Amerom et al.).

[0335] Figure 9 A cross-section of the eighth ion-molecule reactor 900 is shown, which is partially similar to Figure 2 the second ion-molecule reactor 200 shown. Specifically, all the elements and components 910, 911, 912, 913, 914, 920, 921, 922, 923, 930a, 930b, 931, 940, and 941 of the eighth reactor 900 correspond to the elements and components 210, 211, 212, 213, 214, 220, 221, 222, 223, 230a, 230b, 231, 240, and 241 of the second reactor 200. For example, the analyte inlet 920 of the eighth ion-molecule reactor 800 is the same as the analyte inlet 220 of the second ion-molecule reactor 200, and so on.

[0336] However, the ion-molecule reactor 900 does not include any rod-shaped electrodes within the housing 910. Instead, the eighth reactor 900 includes an ion funnel 980 that is located within the reaction volume 940, near the analyte inlet 920 and the reagent ion inlets 930a, 930b, and is arranged coaxially with respect to the longitudinal axis 911. The ion funnel 940 consists of four toroidal electrodes, which are Figure 3 , Figure 7 and Figure 10 substantially the same as the ion funnels 380, 780 shown and operate in a similar manner.

[0337] Furthermore, for the eighth ion molecule reactor 900, each reagent ion inlet 930a, 930b includes guiding elements 990a, 990b for guiding the reagent ions 931 before the reagent ions 931 enter the reaction volume 940. The guiding elements 990a, 990b are composed of, for example, four rod-shaped electrodes regularly arranged around the reagent ion inlets 930a, 930b. Thus, the opposite electrodes are connected in parallel, and a pure RF voltage with a normal frequency of 0.1 - 10 MHz is applied between adjacent electrodes. Thereby, a multipole guiding field is generated, which allows the reagent ions 931 to be correspondingly guided and concentrated before the reagent ions 931 enter the internal volume of the housing 910 or the reaction volume 940.

[0338] To apply an appropriate voltage to the ion funnel 980, a first voltage generating device 901 with RF voltage and DC voltage outputs is connected to the electrodes of the ion funnel 980. Another voltage generating device 902 is connected to the guiding elements 990a, 990b, which allows an appropriate voltage to be supplied to the guiding elements 990a, 990b.

[0339] Figure 12 A cross-sectional view along the longitudinal axis of the headspace sampler 1200 is shown. The sampler 1200 includes a hollow cylindrical container 1210 with a circular bottom surface. The upper end face side 1212 of the container 1210 is closed except for an outlet opening in the form of a short connecting piece 1215 with a central hole, while the opposite lower end face of the container 1210 has a centered and circular opening 1213. Near the lower end face, a fritted ring 1214 is embedded in the side cylindrical wall of the container 1210. Thus, the fritted ring 1214 is arranged concentrically with respect to the longitudinal axis of the container 1210.

[0340] The fritted ring 1214 is made of a gas-permeable fritted material, which allows fluid communication through the wall of the container 1210.

[0341] Except for the fritted ring 1214, the sampler 1200 is made of, for example, stainless steel.

[0342] The container 1210 is included within a spaced-apart tubular cylindrical housing 1220 such that there is a closed annular free volume 1224 around the side surface 1216 of the container 1210. A short connector 1215 of the container 1210 extends through the upper end face 1222 of the housing 1220. The lower end face 1223 of the housing has a centered and circular opening that has the same dimensions as the circular opening 1213 of the container 1210. An inlet in the form of a short connector 1221 is provided in the side wall of the housing 1220 that allows fluid to be introduced into the free volume 1224 between the container 1210 and the housing 1220. Inside the free volume 1224, the fluid can be heated by the side surface 1216 of the container 1210 and, in turn, can heat through the side surface 1216 of the container 1210. Accordingly, this arrangement represents a heat exchange element.

[0343] Also as Figure 12 shown, a cylindrical cork 1250 having a diameter smaller than the inner diameter of the container 1210 can be partially placed inside the container 1210 through the opening 1213. The cork 1250 does not contact any element of the sampler 1200 and there is a free passage between the cork 1205 and the container 1210 such that the interior of the container is freely in communication with the exterior of the sampler 1200. Accordingly, with this non-gas-tight closed arrangement, overpressure relief is achieved.

[0344] In operation, the container can be heated to a high temperature, such as 150 °C, with a heating element (not shown) that is, for example, embedded within the wall of the container 1210. Thereby, the analyte 1251 (such as TCA) included in the cork 1250 and possibly at least some other substances 1253 are evaporated (represented by the dashed arrows) and accumulate in the form of gaseous analyte 1252 and other gaseous substances 1254 around the outer surface of the cork 1250.

[0345] Simultaneously, a carrier gas 1260 (such as N 2 ) is conveyed through the connector 1221 into the free volume 1224 where the carrier gas 1260 is heated by the side surface 1216 of the container 1210. The heated carrier gas 1261 then enters the interior of the container 1210 through the fritted ring 1214 and moves along the surface of the cork 1250 inside the container 1210 whereby the gaseous analyte 1252 and other gaseous substances 1254 are mixed with the heated carrier gas 1261 and transported towards the outlet or short connector 1215. Due to the free passage in the region of the lower end face side 1211 of the container 1210, any overpressure of the carrier gas 1261 or any overpressure inside the container 1210 will be automatically released accordingly.

[0346] Thus, the gaseous mixture 1263, which consists of the heated carrier gas 1261, the analyte 1252, and other substances 1254, leaves the short connection piece 1215 of the sampler 1200.

[0347] Figure 13 shows Figure 12 a schematic diagram of the sampler 1200 connected to Figure 5 the device shown. Specifically, the gaseous mixture 1263 leaving the outlet 1215 of the sampler 1200 is introduced via the analyte inlet 220 Figure 2 into the second ion-molecule reactor 200 shown. Thus, the gaseous mixture 1263 represents Figure 2 the analyte 221 shown.

[0348] Once chemically ionized in the ion-molecule reactor 200, analyte ions and ions of other substances are generated in the second ion-molecule reactor 200, where NO + is preferably used as the reagent ion 231 for the analysis of halobenzenes (such as TCA) in corks. Preferably, the pressure in the ion-molecule reactor 200 is 1 - 5 mbar.

[0349] The analyte ions and ions of other substances emerging from the circular opening 212 of the ion-molecule reactor are fed into an optional differential pumping interface 501 to further reduce the pressure and then into a mass analyzer 502, such as a time-of-flight mass analyzer.

[0350] In Figure 14 is shown a schematic diagram of the automatic sampling unit 1400. The sampling unit includes a conveyor belt 1410, which can be loaded with corks 1450, 1451, 1452, 1452, and can move step by step towards Figure 14 the right side. The sampler 1200 is mounted on a linear manipulator 1420, which is capable of moving the sampler 1200 up and down to place the sampler 1200 above the cork and then take a sample from the cork.

[0351] In Figure 14 is shown the sampler 1200 in a position above a specific cork 1452 to be analyzed. Thus, as Figure 13 explained, for example, the gaseous mixture 1263, which especially contains the analyte of interest, is transported to the ion-molecule reactor.

[0352] Once the analysis of the specific cork 1452 is completed, the manipulator 1420 will move the sampler 1200 upward to the holding position (indicated by the dashed line). When the sampler 1200 is in the holding position, the conveyor belt 1410 will move to the right, thereby placing the next cork 1451 to be analyzed under the sampler 1200. Thus, the cork 1452 will move to Figure 14 the right side, where the other corks 1453 that have been analyzed are located.

[0353] Then, the manipulator 1420 will move the sampler 1200 downward so that the next cork 1451 can be analyzed. Subsequently, the remaining corks 1450 can be processed in the same manner.

[0354] Therefore, the sampling unit 1400 is configured to collect at least one analyte from each sample and introduce at least one analyte from each sample sequentially into the reaction volume of the ion molecule reactor.

[0355] Figure 15 Device 1500 is shown having four samplers 1200a, 1200b, 1200c, 1200d and a multi-port valve 1520. The multi-port valve 1520 includes four valve inlets 1521, 1522, 1523, 1524 and two valve outlets 1525, 1526. All the samplers 1200a, 1200b, 1200c, 1200d are Figure 12 identical in structure to the sampler 1200 shown. Each of the four samplers 1200a, 1200b, 1200c, 1200d is connected via a gas conduit to one of the four valve inlets 1521, 1522, 1523, 1524 through its outlet 1215a, 1215b, 1215c, 1215d.

[0356] Using the multi-port valve 1520, the samples previously placed in the samplers 1200a, 1200b, 1200c, 1200d can be analyzed sequentially by internally connecting each valve inlet 1521, 1522, 1523, 1524 to the valve outlet 1526, which in turn can be connected to the ion molecule reactor. The second outlet 1526 of the multi-port valve 1526 can be used, for example, to flush the multi-port valve and the sampler.

[0357] Therefore, using the multi-port valve 1520, multiple samples can be loaded into the multiple samplers 1200a, 1200b, 1200c, 1200d in parallel, and the analytes collected in each of the multiple samplers can be introduced into the ion molecule reactor sequentially or simultaneously.

[0358] Figure 16aThe sample holder 1600 that can be used in a sampling unit is shown in a top view, while Figure 16b shows a cross-section of the sample holder 1600 taken along Figure 16a line A-A in

[0359] The sample holder 1600 consists of a hollow cylinder 1601 having 10 regularly spaced chambers 1611, 1612, 1613, 1614, 1615, 1616, 1617, 1618, 1619, 1620, which are designed as cylindrical holes, and the longitudinal axes of the cylindrical holes extend from the lower end face 1602 to the upper end face 1603 of the hollow cylinder 1601 in a direction parallel to the longitudinal axis of the hollow cylinder 1601. Each of the chambers 1611 - 1620 has an inlet 1611.2, 1612.2, 1613.2, 1614.2, 1615.2, 1616.2, 1617.2, 1618.2, 1619.2, 1620.2 in the upper end face 1603 and an outlet 1611.1, 1612.1, 1613.1, 1614.1, 1615.1 (the outlets of chambers 1616, 1617, 1618, 1619 and 1620 are not shown in Figure 16a and Figure 16b ). The hollow cylinder 1601 is made of aluminum, for example.

[0360] Between the inlets 1611.2 - 1620.2 of the chambers 1611 - 1620, there are 10 regularly spaced stop grooves 1630a, 1630b, 1630c, 1630d, 1630e, 1630f, 1630g, 1630h, 1630i, 1630j in the upper end face 1603, which start from the radially outer region of the upper end face 1603 and extend in the radial direction towards the inner edge of the upper end face 1603. Similarly, between the outlets 1611.1 - 1620.1 of the chambers 1611 - 1620, there are 10 regularly spaced stop grooves 1620a, 1620b, 1620c, 1620d, 1620e, 1630f (the grooves between chambers 1616 / 1617, 1617 / 1618, 1618 / 1619 and 1619 / 1620 are not shown in Figure 16a and Figure 16b ) in the lower end face 1602, which start from the radially outer region of the upper end face and extend in the radial direction towards the inner edge of the upper end face 1602.

[0361] As Figure 16a and Figure 16bAs shown, there is a circular groove 1603a in the upper end face 1603 around the inlets 1611.2 - 1620.2 of the chambers 1611 - 1620. The circular groove 1603a interconnects all the stop grooves 1630a - 1630j at their radially outer ends, such that the gaseous fluid can be fed from the circular groove 1603a into the stop grooves 1630a - 1630j. Similarly, there is a circular groove 1602a in the lower end face 1602 around the outlets 1611.1 - 1620.1 of the chambers 1611 - 1620. The circular groove 1602a interconnects all the stop grooves 1620a - 1620j, such that the gaseous fluid can be fed from the circular groove 1602a into the stop grooves 1620a - 1620j.

[0362] Figure 17a The device including Figure 16a the sample holder 1600 is shown in a top view, while Figure 17b the details of the device 1700 along the Figure 17a dashed line in the cross - sectional view are shown. Thus, the inlet closing member 1702 covering the chambers 1611 - 1618 is arranged on top of the upper end face 1603 (the chambers 1619 and 1620 are not covered). The inlet closing member 1702 consists of a solid ring - segment - shaped disk, for example made of polytetrafluoroethylene (PTFE), and its width is similar to the width of the upper end face 1603. For each of the chambers 1611 - 1618 covered by the inlet closing member 1702, the inlet closing member 1702 includes through - openings 1702.1, 1702.2, 1702.3, 1702.4, 1702.5, 1702.6, 1702.7, 1702.8. In the Figure 17a 、 Figure 17b configuration shown, the through - openings 1702.1 - 1702.8 are centered above the chambers 1611 - 1618, such that the chambers 1611 - 1618 are open on the inlet side. Additionally, the inlet closing member 1702 includes at least one opening 1740 located above the circular groove 1603a for delivering the gaseous fluid to the circular groove 1603a.

[0363] Similarly, the outlet closing member 1701 is arranged below the lower end face 1602. The outlet closing member 1701 also consists of a solid annular disk, for example made of polytetrafluoroethylene (PTFE), and has a shape similar to that of the inlet closing member 1702. For each of the chambers 1611 - 1618 covered by the outlet closing member (the chambers 1619 and 1620 are not covered), the outlet closing member 1701 includes through - openings 1701.1, 1701.2 ······ 1701.8. In the Figure 17aIn the configuration shown, the through openings 1701.1 - 1701.8 are centered below the chambers 1611 - 1618 such that the chambers 1611 - 1618 are open on the exit side. Additionally, the exit closure member 1701 includes an opening (not shown) above the circular recess 1602a for delivering a gaseous fluid into the circular recess 1602a.

[0364] Additionally, Figure 17a and Figure 17b The apparatus shown includes a removal station 1710 for recovering analytes evaporated from a sample S1 (schematically indicated by the dashed line) in the chamber 1611 and removing these analytes from the sampling unit. The removal station 1710 includes a gas inlet 1711 that is located above the chamber 1611 on top of the inlet closure member 1702 and is in fluid communication with the through opening 1702.1. Since the through opening 1702.1 is also in fluid communication with the chamber 1611, a carrier gas can be introduced into the chamber 1611. The sampler outlet 1712 is located below the exit closure member 1701 in the region of the chamber 1611 and is in fluid communication with the through opening 1701.1. Since the through opening 1701.1 is additionally in fluid communication with the chamber 1611, a gaseous fluid can be recovered from the chamber 1611.

[0365] Thus, in Figure 17a 、 Figure 17b the configuration shown, a carrier gas stream is introduced into the chamber 1611 through the gas inlet 1711, and analytes evaporated from the sample S1 can be removed via the sampler outlet 1712. If the sampler outlet 1712 is connected to the analyte inlet of an ion - molecule reactor, the analytes can be directly fed into the ion - molecule reactor, such as the ion - molecule reactors 100, 200, 300, 400, 700, 800, or 900 as described above.

[0366] Meanwhile, the chambers 1612 - 1618 can be flushed with a low - flow gaseous fluid through the openings 1702.2, 1702.3, 1702.4, 1702.5, 1702.6, 1702.7, 1702.8 of the inlet closure member 1702 and through the openings 1701.2, 1701.3, 1701.4, 1701.5, 1701.6, 1701.7, 1701.8 of the exit closure member 1701.

[0367] In Figure 17a 、 Figure 17b the configuration, the chambers 1619 and 1620 that are not covered by the inlet closure member 1702 and the exit closure member 1701 are freely accessible, for example, for loading or unloading samples.

[0368] Additionally, Figure 17a 、Figure 17b The device shown in Figure 17a includes a heating unit having a controller, a heating element, and a temperature sensor ( Figure 17b not shown in

[0369] ), and the temperature sensor is used to set a predetermined constant of the sample holder 1600, such as a temperature of about 130 °C. During operation, a gaseous fluid (such as hot air) is introduced into the grooves 1620a-1620j and 1630a-1630j to create a curtain between adjacent chambers to reduce cross-contamination between samples. Thus, air is delivered via the channels 1620a.1, 1620f.1, 1630a.1, 1630f.1 to the grooves 1630a and 1630f, and similarly to the other grooves.

[0370] In Figure 17a and Figure 17b of the device, the sample holder 1600 is rotatably mounted between an inlet closing member 1702 and an outlet closing member 1701 fixed in place. Thus, by rotating the sample holder 1600, the through-opening of the inlet closing member 1702 and the through-opening of the outlet closing member 1701 can be positioned above a part of the inlet opening or the outlet opening of the corresponding chamber closely adjacent to the sample holder 1600. This situation is shown in Figure 17c . Thus, in this case, all the chambers covered by the inlet closing member 1702 and the outlet closing member 1701 (such as chambers 1611, 1612, 1613) are closed. Therefore, the sides of the inlet closing member 1702 and the outlet closing member 1701 facing the chambers (the inward-facing sides) can be cleaned with air flowing through and escaping from the grooves 1620a-1620f and 1630a-1630f covered by the inlet closing member 1702 and the outlet closing member 1701.

[0371] Specifically, when the sample holder 1600 moves, the inward-facing sides of the inlet closing member 1702 and the outlet closing member 1701 are always cleaned with air flowing through the grooves 1630a-1630j. The cleaning air sweeps across the entire surface exposed to the samples between different samples.

[0372] When the sample holder 1600 is further rotated, a position can be reached where the through-opening of the inlet closing member 1702 is in fluid communication with the grooves (such as 1620a-d and 1630a-d) covered by the inlet closing member 1702 or the outlet closing member 1701. This situation is shown in Figure 17dAs shown. Thus, the through openings (e.g., 1701.1, 1701.2, 1701.3) of the outlet closing member 1701 and the sampler outlet 1712 can be flushed and cleaned with gas. Additionally, this position allows for reference measurements or zero measurements accordingly.

[0373] Figure 18 A schematic view of an apparatus 1800 for measuring an analyte from a solid sample (such as a cork) is shown. As Figure 17a , Figure 17b shown, the device is installed in the apparatus 1800. Thereby, the inlet closing member 1702 and the outlet closing member 1701 are enclosed in an annular-segment-shaped housing 1810, which allows the conveyance of a gaseous fluid to the inlet closing member and the discharge of the gaseous fluid from the outlet closing member. The sampler outlet 1712 is connected to an ion-molecule reactor 1830, which is, for example, structurally the same as the ion-molecule reactors 100, 200, 300, 400, 700, 800, or 900 described above.

[0374] Additionally, the apparatus 1800 includes a preheating station 1820 in which a plurality of samples S can be preheated to a constant temperature. The preheating station includes a controller, a heating element, and a temperature sensor (not shown), and the temperature sensor is used to set a predetermined constant temperature. The heating is achieved, for example, by a hot air generating device (not shown).

[0375] The apparatus 1800 further includes a loading unit 1821 for placing each sample S in a chamber of the sample holder and / or for removing the sample from the chamber. The loading unit 1821 is placed near an area of the sample holder 1600 that is not enclosed by the housing 1810. Thus, in this area, the sample can be directly introduced into the freely accessible chambers (e.g., chambers 1611 and 1612 in this configuration). By rotating the sample holder 1600, different chambers can be loaded or unloaded in sequence.

[0376] Figure 19 A perspective view of a preheating station 1900 is shown, which can be used, for example, in an Figure 18 apparatus. The preheating station 1900 includes a serpentine path 1920 on a platform, and a chain 1921 of interconnected and open receivers for respective samples (details are shown in Figure 20 ) is movably mounted on the serpentine path 1920. The chain 1921 is driven by an electric gear and redirected multiple times through idler gears. A supply station 1923 allows the introduction of cork samples into the receivers. The preheating station 1900 further includes a cover 1925, and the cover 1925 includes two hot air generating devices 1924. If the cover 1925 is closed, the hot air flows around the samples in the receivers.

[0377] In addition, the loading unit 1922 is integrated in the preheating station 1900 (see Figure 19 in the upper left side). In operation, a chain 1921 of interconnected and open receivers moves over the loading unit. At defined positions, there are openings in the path 1920 of the preheating station such that the individual samples from the receivers located above the openings can move out of the receivers downward under the action of gravity. If the preheating station is placed appropriately above the sample holder, for example Figure 18 as shown, the sample can be introduced directly into the chamber of the sample holder.

[0378] Between the loading unit 1922 and the supply station 1923, the receivers are cleaned, for example with hot air, before introducing a new cork sample. Additionally or alternatively, the receivers can be cleaned with another gas, liquid, and / or mechanically.

[0379] Figure 20 A part of the movable chain 1921 of Figure 19 is shown in detail. The movable chain 1921 includes a series of cylindrical pipe fittings 1921.1a, 1921.1b, which are held together by a pair of outer links 1921.2a, and the outer links alternate with a pair of inner links 1921.2b. The outer links 1921.2a and the inner links are pivotable relative to each other. Additionally, the chain 1921 includes lateral flanges 1921.3 to better guide the chain. The cylindrical pipe fittings 1921.1a, 1921.1b are open at both ends and receive samples, such as corks, therein.

[0380] With the aid of a suitable control unit, the preheating station 1900 can be operated in a synchronized manner with a sampling unit (for example, the sampling unit 1700).

[0381] Although the ion molecule reactors, mass spectrometers, samplers, devices, equipment, and methods described herein constitute preferred embodiments of the present invention, it should be understood that the present invention is not limited to these embodiments and changes can be made therein without departing from the scope of the present invention.

[0382] For example, in all ion molecule reactors 100, 200, 300, 400, 700, 800, 900, different and / or additional ion guides and / or electrode assemblies can be used to guide and / or concentrate ions along a predetermined transport path.

[0383] For example, instead of the quadrupole devices used in reactors 100, 200, 300, 400, octopole devices or devices with any other number of rod electrodes can be used. A combined quadrupole / octopole device can also be suitable. Additionally, in all ion molecule reactors, for example, additional ring electrodes can be attached inside and / or outside the housing.

[0384] In all ion-molecule reactors 100, 200, 300, 400, 700, a cylindrical rod-shaped electrode can be arranged, for example, inside a housing. Instead of an external cylindrical rod-shaped electrode, a housing with an electrode integrated in the housing wall can also be used. For ion-molecule reactors 800, 900, additional ion guides in the form of multipole electrodes can be added, for example, to further guide ions inside or outside the reaction volume.

[0385] Moreover, the dimensions, shapes, and numbers of the electrodes described in the exemplary embodiments can be different. For example, Figure 1 、 Figure 2 、 Figure 3 、 Figure 4 and Figure 7 the rod-shaped electrodes described can have a non-circular cross-section. Additionally, if desired, the number and shape of the electrodes of the ion funnels or ion blankets described in Figure 3 、 Figure 7 、 Figure 8 、 Figure 10 and Figure 11 can be changed.

[0386] Although in the ion-molecule reactors herein, a predetermined transport path is defined linearly along the longitudinal axis, a transport path extending along a non-longitudinal axis and / or a transport path having a curved portion is also possible.

[0387] Furthermore, reagent ion inlets and / or reagent ion sources with other geometries can be envisioned. For example, in the Figure 2 embodiment, a reagent ion inlet with an annular nozzle can be used instead of two separate inlets 230a, 230b. More than two separate inlets can also be envisioned, such as 3, 4, 5, 7, or even more inlets, which are preferably arranged symmetrically around the reaction volume.

[0388] Regarding the shape of the housing, non-cylindrical shapes, such as a cubic housing or even more complex shapes, are also possible. The specific dimensions and proportions of the housing of the ion-molecule reactor are not limited at all and can be adapted to specific requirements if needed.

[0389] Moreover, the housing can be made of at least partially or completely flexible or bendable material, such as made of plastic material. In a specific embodiment, the ion-molecule reactor or its housing can correspondingly be made of a bendable tube. Such a device allows, for example, the effective transport of ions over a relatively long distance (e.g., several meters). The embodiment with a bendable tube enables, for example, the ion-molecule reactor to be correspondingly used as a probe or probe head for collecting analyte samples at any position, for example, similar to a vacuum cleaner.

[0390] If desired, components for heating and / or cooling can be included in the ion-molecule reactor, which for example allows heating and / or cooling of the housing.

[0391] Similarly, in Figure 3 and Figure 4 the permeable part in the illustrated embodiment can be used to introduce sheath gas to further reduce wall effects.

[0392] In particular, in the Figure 3 embodiment, the permeable part 360 can be used to introduce sheath gas rather than removing neutrals from the reaction volume. This is a selective method for reducing wall effects in the ion-molecule reactor. Thus, the permeable part 360 can cover the entire cylindrical surface area of the housing 310 within the outer tubular element 370. Compared to prior art systems with laminar flow using sheath gas with a relatively high pressure, the device of the present invention results in a much lower pressure in the reaction volume.

[0393] Furthermore, in the Figure 6 embodiment, reagent inlets as shown in Figure 1 or Figure 3 can be envisaged. In this case, instead of introducing reagent ions through the permeable part 660, sheath gas can be introduced into the housing 610 to reduce wall effects in the ion-molecule reactor.

[0394] Moreover, Figure 12 the sampler 1200 shown can have different geometries, for example it can have a cubic container. The outer housing 1220 can also be omitted and the carrier gas 1260 can be introduced directly through the fritted ring 1214. Thereby, the carrier gas 1260 can be preheated, for example, with an external heater.

[0395] The container 1210 can also be designed such that a complete sample (such as a cork) can occupy the interior of the container. Thus, closures can be provided to seal the container either hermetically or non-hermetically. For non-hermetic closures, a lid with a permeable membrane or part can be used.

[0396] Regarding the Figure 14 automatic sampling unit 1400, several samplers 1200 can be arranged, for example, on the manipulator 1420. In this case, several samples can be preheated and / or analyzed in parallel. Thus, it can be advantageous to use a multi-port valve 1520 as shown in Figure 15 to connect the individual samplers to the ion-molecule reactor.

[0397] Instead of the Figure 14 linear manipulator 1420 shown, a two-axis or three-axis manipulator or robotic arm can be used. Additionally, a circular manipulator can be used. Thus, the conveyor belt can be omitted if desired.

[0398] In addition, a second ion-molecule reactor can be attached at the second valve outlet 1525 of the multi-port valve 1520 to enable the measurement of several samples in parallel. This parallel processing can help to further increase the throughput. Additionally, if the multi-port valve has other outlets, additional ion-molecule reactors can be attached.

[0399] Instead of Figure 16a 、 Figure 16b the sample holder 1600 shown, a sample holder with more or fewer than 10 chambers, for example with 50, 75 or 100 chambers, can be used. Additionally, the sample holder 1600 does not necessarily have to be circular. In principle, a straight sample holder can be provided.

[0400] Figure 19 The preheating station 1900 shown can also be different in design. For example, instead of or in addition to the hot air generating device, one or more heating rods can be used. The chain 1921 can also be replaced by another transport device (such as a conveyor belt). Additionally, a manipulator can be used to remove the sample from the receiver and / or place the sample into the chambers of the sample holder. In this case, the sample can also be placed in a receiver with a closed end and / or fixed in a fixed receiver in the preheating station.

[0401] In summary, it should be noted that a very advantageous arrangement for the ion-molecule reactor and the sampler is provided, which allows a significant increase in the efficiency of chemical ionization and provides the ionized analyte in surprisingly high yields. In particular, due to the ion-molecule reactor, mass spectrometer, sampler, device, equipment and method of the present invention, analytes can be detected and analyzed with high sensitivity and allow for a high sample throughput, for example, as required for detecting cork taint and / or halogenated anisoles in corks.

Claims

1. A sampling unit having a sampler for collecting at least one analyte from a sample, the sampling unit being capable of sequentially collecting analytes from respective samples from a plurality of samples, wherein the sampling unit includes a sample holder (1600) having a number of chambers (1611 - 1620), wherein, each chamber is configured to receive a single sample, wherein each chamber includes an inlet (1611.2 - 1620.2) and an outlet (1611.1 - 1620.1) such that a gaseous fluid flow can pass through each chamber, the sample holder includes an inlet closing member (1702) and an outlet closing member (1701), the inlet closing member (1702) is configured to close and open at least a part of the inlet of the chamber, the outlet closing member (1701) is configured to close and open at least a part of the outlet of the chamber, wherein the inlet closing member (1702) and / or the outlet closing member (1701) is movable relative to the sample holder and vice versa, such that once there is relative movement between the sample holder (1600) and the inlet closing member (1702) and / or the outlet closing member (1701), at least a part of the inlet of the chamber and / or at least a part of the outlet of the chamber can be opened or closed simultaneously.

2. The sampling unit according to claim 1, wherein, the sample is a solid sample.

3. The sampling unit according to claim 1, wherein, the sample is a cork.

4. The sampling unit according to any one of claims 1 - 3, including channels (1620a - 1620j, 1630a - 1630j) between adjacent chambers, wherein, the channels are configured to create a curtain of gaseous fluid between adjacent chambers to at least partially separate the inlets (1611.2 - 1620.2) and / or outlets (1611.1 - 1620.1) of adjacent chambers.

5. The sampling unit according to any one of claims 1 - 3, including at least one removal station (1710) for separately recovering the analyte evaporated from the sample (S1) in the chamber and removing the analyte from the sampling unit.

6. The sampling unit according to claim 5, wherein the analyte is removed from the sampling unit via a sampler outlet (1712).

7. The sampling unit according to any one of claims 1 - 3, wherein, the sample holder (1600) includes a hollow cylinder (1601), wherein the chambers (1611 - 1620) are present in the wall of the hollow cylinder.

8. The sampling unit according to claim 7, wherein, the hollow cylinder is a hollow annular cylinder.

9. The sampling unit according to claim 7, wherein, the sample holder is rotatably mounted between the inlet closing member (1702) and the outlet closing member (1701).

10. The sampling unit according to any one of claims 1 - 3, wherein, The sampling unit further includes a preheating station (1820, 1900) configured such that in operation a gaseous fluid flows around the sample.

11. The sampling unit according to claim 10, wherein, the preheating station (1820, 1900) further includes a loading unit (1821, 1922) for placing respective samples in the chambers of the sample holder (1600), wherein the loading unit (1922) includes a series of receivers (1921.1a, 1921.1b) in the form of cylindrical pipe fittings, and the cylindrical pipe fittings are held together by links (1921.2a, 1921.2b) pivotable around the cylindrical pipe fittings.

12. A kit, comprising an ion-molecule reactor or a mass spectrometer, and a sampling unit according to any one of claims 1-11 having a sampler for collecting at least one analyte from a sample.

13. The kit according to claim 12, wherein, the sampler is a headspace sampler.

14. The kit according to claim 13, wherein, the sampler includes a hollow body.

15. The kit according to claim 14, wherein, the hollow body is a container.

16. The kit according to claim 14, wherein, the hollow body is a bottle.

17. The kit according to claim 14, wherein, the hollow body is a hollow tube.

18. The kit according to any one of claims 12 to 14, wherein, the sampler includes a heatable container for receiving a sample, an inlet for introducing a gaseous fluid into the interior of the container, and an outlet for recovering the gaseous fluid from the sampler.

19. The kit according to claim 15, wherein, the container includes an opening for inserting the sample into the container.

20. The kit according to claim 19, wherein, the edge of the opening is configured to encapsulate the sample in a given contact area when the sample is placed in the container.

21. The kit according to claim 18, wherein, the sampler includes a heating element that allows heating of the container.

22. The kit according to claim 21, wherein, the heating element allows heating of the container to a temperature of 20 - 300 °C.

23. The kit according to claim 21, wherein, the heating element allows heating of the container to a temperature of 30 - 100 °C.

24. The kit according to claim 21, wherein, the heating element allows heating of the container to a temperature of 40 - 75 °C.

25. The kit according to claim 18, wherein, the sampler includes a heat exchanger element for preheating the gaseous fluid before it enters the inlet.

26. The kit according to claim 25, wherein, the heat exchanger element allows the gaseous fluid to contact the outer surface of the container before entering the inlet.

27. The kit according to claim 18, wherein, the container comprises a single-ended closed tubular container.

28. The kit according to claim 27, wherein, the outlet is in the end face of the single-ended closed tubular container and / or the inlet is in the side surface of the single-ended closed tubular container.

29. The kit according to claim 27, wherein, the single-ended closed tubular container is included within a spaced-apart tubular housing such that there is a closed free volume around the side surface of the single-ended closed tubular container and such that the open end of the single-ended closed tubular container remains freely accessible from the outside.

30. The kit according to claim 15, wherein, the container comprises an overpressure discharge port, a breathable part and / or a breathable closure.

31. The kit according to claim 30, wherein, the breathable part and / or the breathable closure is placed inside the inlet and protrudes from the inlet towards the inside of the container.

32. The kit according to claim 30 or 31, wherein, the breathable part and / or the breathable closure is annular.

33. The kit according to claim 32, wherein, the breathable part and / or the breathable closure is an annular frit.

34. The kit according to any one of claims 12 - 17, wherein the sampling unit is capable of loading a plurality of samples into the sampler sequentially.

35. The kit according to claim 34, wherein, the sampling unit is an automatic sampling unit.

36. The kit according to claim 34, wherein, the sampling unit is configured to collect at least one analyte from each sample and introduce at least one analyte from each sample sequentially into the reaction volume of the ion molecule reactor.

37. An apparatus for analyzing a sample, the apparatus comprising the kit according to any one of claims 12 - 36, wherein, the sampler is connected to the analyte inlet of the ion molecule reactor.

38. A method for generating analyte ions using a sampling unit having a sampler for collecting at least one analyte from a sample and an ion molecule reactor (100, 300) according to any one of claims 1 - 11, the method comprising the steps of: a) introducing an analyte (121, 321) into the reaction volume (140, 340) of the chamber through the analyte inlet (120, 320) of the ion reactor; b) providing reagent ions (131, 331) and introducing the reagent ions into the reaction volume (140, 340); c) causing the reagent ions (131, 331) to interact with the analyte (121, 321) to form analyte ions (123, 323); d) using an alternating electric field, magnetic field or electromagnetic field, guiding the reagent ions and / or analyte ions along a predetermined transport path (141, 341) through the reaction volume (140, 340) using an ion guide (150, 151, 350, 351); Wherein, the analyte (121, 321) is introduced into the reaction volume (140, 340) along an inlet path (122, 322), wherein the direction of the inlet path extends substantially along at least a first portion of a predetermined transport path (141, 341) in the reaction volume (140, 340).

39. The method according to claim 38, wherein the analyte is introduced into the reaction volume in the form of a mixture with at least one other chemical substance.

40. The method according to claim 39, wherein the analyte is introduced into the reaction volume in the form of a mixture with a plurality of other chemical substances.

41. The method according to claim 39, wherein the analyte is introduced into the reaction volume in the form of a mixture with at least 5 different other chemical substances.

42. The method according to claim 39, wherein the analyte is introduced into the reaction volume in the form of a mixture with at least 10 different other chemical substances.

43. The method according to claim 39, wherein the analyte is introduced into the reaction chamber in the form of a mixture with at least 100 different other chemical substances.

44. The method according to any one of claims 39 - 43, wherein, the mixture comprises or consists of a vapor that contains substances evaporated from cork.

45. The method according to any one of claims 39 - 43, wherein, the mixture comprises or consists of a vapor that contains substances evaporated from a cork stopper.

46. The method according to any one of claims 38 - 43, wherein, the analyte comprises or consists of a halogenated cresol and / or a halogenated phenol.

47. The method according to any one of claims 38 - 43, wherein, the analyte comprises at least one compound selected from the group consisting of 2,4,6 - trichloroanisole (TCA), 2,3,4,6 - tetrachloroanisole (TeCA), 2,3,4,5,6 - pentachloroanisole (PCA), and 2,4,6 - tribromoanisole (TBA), or consists of at least one compound selected from the group consisting of 2,4,6 - trichloroanisole (TCA), 2,3,4,6 - tetrachloroanisole (TeCA), 2,3,4,5,6 - pentachloroanisole (PCA), and 2,4,6 - tribromoanisole (TBA).

48. The method according to any one of claims 39 - 43, wherein, the mixture further comprises a carrier gas.

49. The method according to claim 48, wherein, the carrier gas is an inert gas.

50. The method according to claim 48, wherein, the carrier gas is Kr and / or Ar.

51. The method according to any one of claims 38 - 43, wherein, the pressure in the ion - molecule reactor (100, 300) is below 500 mbar.

52. The method according to any one of claims 38 - 43, wherein, the pressure in the ion - molecule reactor (100, 300) is below 100 mbar.

53. The method according to any one of claims 38 - 43, wherein, the pressure in the ion - molecule reactor (100, 300) is below 50 mbar.

54. The method according to any one of claims 38 - 43, wherein, the pressure in the ion - molecule reactor (100, 300) is below 10 mbar.

55. The method according to any one of claims 38 - 43, wherein, the pressure in the ion - molecule reactor (100, 300) is below 5 mbar.

56. The method according to any one of claims 38 - 43, wherein, the pressure in the ion - molecule reactor (100, 300) is below 1 mbar.

57. The method according to any one of claims 38 - 43, wherein, the pressure in the ion - molecule reactor (100, 300) is below 0.5 mbar.

58. The method according to any one of claims 38 - 43, wherein, the analyte ions are generated from the analyte and reagent ions by chemical ionization.

59. The method according to any one of claims 38 - 43, wherein, the analyte ions are generated from the analyte and reagent ions by proton - transfer reaction and / or charge - transfer reaction.

60. The method according to claim 56, wherein, The reagent ions are selected such that the population of the unprotonated analyte ions (M + ) formed is greater than the population of the protonated analyte ions (MH + ).

61. The method according to any one of claims 38 - 43, wherein, The reagent ions are selected from NO + and / or O 2 + .

62. The method according to any one of claims 38 - 43, wherein, The reagent ion is NO + .

63. The method according to any one of claims 38 - 43, wherein, the analyte ions generated in the ion - molecule reactor are introduced into a mass analyzer.

64. The method according to claim 63, wherein, the mass analyzer is a time - of - flight mass analyzer, a quadrupole mass analyzer, an ion trap analyzer, a sector - field mass analyzer, and / or a Fourier transform ion cyclotron resonance analyzer.

65. A method for analyzing a sample, the method comprising the steps of: a) collecting at least one analyte from a sample containing at least one analyte using the sampling unit according to any one of claims 1 to 11; b) generating analyte ions from the at least one analyte using the method according to any one of claims 38 - 64; c) analyzing the analyte ions.

66. The method according to claim 65, wherein, the method comprises the step of analyzing the analyte ions using a mass analyzer.

67. The method according to claim 65 or 66, wherein in step a), the at least one analyte is collected by heating under conditions suitable for achieving evaporation of at least one analyte present in the sample.

68. The method according to claim 67, wherein heating the sample and / or collecting the analyte is achieved under constant pressure conditions.

69. The method according to claim 65 or 66, wherein the at least one analyte collected in step a) is mixed with a carrier gas and introduced into the reaction volume as a mixture in step b).

70. The method according to claim 65 or 66, wherein after collection in step a), the analyte collected in step a) is immediately and continuously introduced into the reaction volume in step b).

71. The method according to claim 69, wherein, in order to mix, the carrier gas is guided to flow at least along a part of the surface of the sample.

72. The method according to claim 69, wherein, in order to mix, the carrier gas is guided to flow at least along a part of the surface of the cork.

73. The method according to claim 69, wherein, before mixing, the carrier gas is heated.

74. The method according to claim 69, wherein, before mixing, the carrier gas is heated to a temperature suitable for achieving the evaporation of at least one analyte present in the sample.

75. The method according to claim 69, wherein the mixture containing the at least one analyte ion is introduced into the reaction volume in step b) without otherwise affecting the chemical and / or physical properties of the mixture.

76. The method according to claim 69, wherein the mixture containing the at least one analyte ion is introduced into the reaction volume in step b) without otherwise affecting the chemical and / or physical properties of the mixture, without any additional separation step.

77. The method according to claim 69, wherein, the sampler includes a heatable container for receiving the sample, the container including an opening for inserting the sample into the container, an inlet for introducing a gaseous fluid into the interior of the container, and an outlet for recovering the gaseous fluid.

78. The method according to claim 77, wherein, the shape of the opening of the container is complementary to the shape of one end of the sample, such that when the sample is present in the container, the opening is closed by the sample.

79. The method according to claim 77, wherein the sample is inserted into the opening such that when the sample is present in the container, a free passage is maintained between the container and the sample.

80. The method according to claim 77, wherein, the sample is inserted into the container such that when the sample is placed in the container, the sample does not contact the container.

81. Use of the sampling unit according to any one of claims 1 - 11 in mass spectrometry analysis.

82. Use of the sampling unit according to any one of claims 1 - 11 for analyzing a gaseous mixture containing at least one analyte.

83. The use according to claim 82, wherein the gaseous mixture further contains at least 5 different other chemical substances.

84. The use according to claim 83, wherein the gaseous mixture further contains at least 10 different other chemical substances.

85. The use according to claim 83, wherein the gaseous mixture further contains at least 100 different other chemical substances.

86. The use according to claim 83, wherein the gaseous mixture further contains at least 1000 different other chemical substances.

87. The use according to claim 83, wherein the gaseous mixture further comprises at least 10,000 different other chemical substances.

88. The use according to claim 83, wherein the gaseous mixture comprises at least 100,000 different other chemical substances.

89. The use of the sampling unit according to any one of claims 1 - 11 for analyzing whether a sample contains halophenols and / or halocresols, and / or the ratio of cresols and / or halophenols.

90. The use according to claim 89, wherein the sampler is used for analyzing whether the sample contains 2,4,6 - trichloroanisole (TCA), 2,3,4,6 - tetrachloroanisole (TeCA), 2,3,4,5,6 - pentachloroanisole (PCA) and 2,4,6 - tribromoanisole (TBA), and / or the ratio of 2,4,6 - trichloroanisole (TCA), 2,3,4,6 - tetrachloroanisole (TeCA), 2,3,4,5,6 - pentachloroanisole (PCA) and 2,4,6 - tribromoanisole (TBA).

91. The use of the sampling unit according to any one of claims 1 - 11 for analyzing whether a cork has cork contamination.

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